Hydrosilylation cured organosiloxanes having diluent therein

ABSTRACT

A method of preparing a diluted chain extended organopolysiloxane containing polymer comprising the steps of reacting a pre-formed polymer with a suitable chain extender reactable with terminal groups of the polymer in the presence of a diluent material, a suitable catalyst and optionally an end-blocking agent; and Where required quenching the polymerization process wherein the diluent material is substantially retained within the resulting diluted organopolysiloxane containing polymer. The case additionally relates to products of the process and subsequent applications for the polymer such as for example sealants and rubbers.

RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.11/910,724, filed May 22, 2008, which claims priority to and all theadvantages of International Patent Application No. PCT/GB2006/050073,filed on Apr. 3, 2006, which claims priority to Great Britain PatentApplication Nos. GB 0506939.8 and GB 0516239.1, filed on Apr. 6, 2005and Aug. 6, 2005 respectively, all of which are expressly incorporatedherein by reference.

This invention is concerned with the chain extension of one or morepolymers or oligomers, comprising an at least partiallyorganopolysiloxane containing polymeric chain, in the presence of adiluent to produce a diluted polymer and compositions containing theresulting polymers.

The rheological properties of uncured polymers are primarily a functionof their viscosities. The viscosity of an uncured polymer is directlyrelated to the molecular weight of the polymer and the length of thepolymer chain, usually defined as the degree of polymerisation (dp). Ingeneral the lower the viscosity of a polymer the higher the extrusionrate of uncured compositions which contain the polymer. The viscosity ofthe uncured polymer is also a major influence on several of the physicalproperties of compositions incorporating the polymer such as, forexample, sealant compositions, when such compositions are subsequentlycured.

Organosiloxane compositions which cure to elastomeric solids are wellknown and such compositions can be produced to cure at either roomtemperature in the presence of moisture or with application of heat.Typically those compositions which cure at room temperature in thepresence of moisture are obtained by mixing a polydiorganosiloxane basedpolymer having reactive terminal groups, with a suitable silane (orsiloxane) based cross-linking agent in the presence of one or morefillers and a curing catalyst. These compositions are typically eitherprepared in the form of one-part compositions curable upon exposure toatmospheric moisture at room temperature or two part compositionscurable upon mixing under room conditions.

One important application of the above-described curable compositions istheir use as sealants. In use as a sealant, it is important that thecomposition has a blend of properties which render it capable of beingapplied as a paste to a joint between substrate surfaces where it can beworked, prior to curing, to provide a smooth surfaced mass which willremain in its allotted position until it has cured in to an elastomericbody adherent to the adjacent substrate surfaces. Typically sealantcompositions are designed to cure quickly enough to provide a sound sealwithin several hours but at a speed enabling the applied material to betooled in to a desired configuration shortly after application. Theresulting cured sealant is generally formulated to have a strength andelasticity appropriate for the particular joint concerned.

The introduction of an inorganic filler into an elastomeric compositioncontaining an organopolysiloxane containing polymer is often required toobtain useful tear, durometer, elongation and modulus at 100% elongationproperties. The rheological properties of an uncured elastomer aredependent on filler properties (when a filler is present in thecomposition) such as filler concentration and structure and the degreeof polymer-filler interaction as well as the viscosity of the polymer.In general the lower the viscosity of the uncured organopolysiloxanecontaining composition, optionally containing filler, the higher theextrusion rate of the uncured composition. As a result applicationsrequiring high extrusion rates such as uncured sealants, which in use,are generally extruded manually using a sealant gun or the like, need totypically use low viscosity polymers (e.g. <100 000 mPa·s at 25° C.) toensure suitable composition extrusion rates for manual end uses.

The physical properties of the resulting cured composition effectedinclude elongation and modulus (at 100% elongation) which areparticularly important for sealants used in for example expansion jointsin the construction and transportation industries, where the need forsealants with low modulus and high elongation are essential.

Hence, whilst it is known that increasing the molecular weight of apolymer would improve some physical properties of a sealant, typicallythe maximum viscosity used in current formulations are in practice nogreater than about 150 000 mPa·s at 25° C. Whilst organopolysiloxanepolymers having viscosities of up to 1,000,000 mPa·s at 25° C. have beendiscussed in the prior art the use of such polymers having suchviscosities has been practically and economically unmanageable. Hence,whilst it is known that increasing the molecular weight of the polymerwould improve the some properties of the sealant typically the maximumviscosity used in current formulations are in practice no greater thanabout 150 000 mPa·s at 25° C.

One method used to increase polymer chain lengths is “chain extension”in which after the completion of an initial polymerisation reaction,difunctional intermediates reactive with the polymer end-groups areadded to the resulting polymer with a view to further increasing the dpand molecular weight of the polymer. In sealant applications the chainextender molecules may be reacted with polymer at the same time as thecomposition is cured by interaction with a cross-linker necessitatingcareful selection of chain extender such that the rate of reactionbetween polymer and chain extender is faster than the reaction betweenthe polymer and cross-linker. In the case of sealant type applicationsthis has the advantage of keeping the viscosity of uncured compositionsat a level suitable for manual application of the composition using asealant gun or the like, and that an effective dp and molecular weightincrease occurs during the curing stage after the sealant compositionhas been applied and introduced into air.

Suitable chain extenders are identified as being reactable with thepolymer end groups to generate extended polymers. Typically whilst thismay involve any suitable chemistry, the chain extension of polymers ofthis type usually involves one of two reaction routes, i.e. addition andcondensation chain extension.

In U.S. Pat. No. 3,341,486 Silanol end-blocked polysiloxanes arecombined with di- and triaminoxysilanes or -siloxanes to provide a roomtemperature vulcanisable (RTV) composition that both chain extends andcross-links in the presence of atmospheric moisture. In U.S. Pat. No.4,071,498 a siloxane containing monovalent hydrocarbon or halogenatedhydrocarbon residues and, on average, at least one —OH group. permolecule bonded to Si is mixed withmethylvinyldi(epsilon-caprolactamo)silane. The resulting organosiloxaneisolated had a higher molecular weight than the original organosiloxaneand contains methylvinylsiloxane units. U.S. Pat. No. 4,614,760describes a one-part silicone elastomeric composition that is flowableor easily extruded is prepared by mixing a hydroxyl end-blockedpolydiorganosiloxane, a difunctional silane having two amido radicals,and an organic peroxide suitable for vulcanizing silicone rubber. Uponapplication the composition is exposed to moisture to activate a chainextension reaction. U.S. Pat. No. 5,914,382 describes a method of chainextending α,Ω-dihydroxypoly(diorganosiloxanes) comprises reacting lowmolecular weight α,Ω-dihydroxypoly(diorganosiloxanes) with phosphateester(s) and/or H₃PO₄. EP0909778 describes the preparation ofchain-extended organopolysiloxanes from organopolysiloxanes having atleast one silicon-bonded hydroxyl group per polymer molecule, by addinga nitrogen-containing silylating agent which is capable of bothchain-extending and silylating the organopolysiloxanes with anitrogen-containing silylating agent capable of chain-extension toproduce a chain-extended organopolysiloxane. US2004/0122199 describesorganopolysiloxane compositions comprising organopolysiloxanes which areterminated at both ends by Si-bonded hydroxy groups, at least onedialkylaminomethylalkyldialkoxysilane chain extender and/or partialhydrolysates thereof, (d) at least one isocyanurate deactivator, andoptionally plasticiser, a silane cross-linker and/or one or morecatalysts for accelerating the reaction of the silane cross-linker withSi—OH groups on the polymer. EP0651022 describes a curableorganosiloxane composition comprising an organopolysiloxane polymerhaving vinyl end-groups a chain extender containing a silane or shortchain siloxane having two Si—H groups, a cross-linking agent and aplatinum based catalyst.

It has become common practice in the formulation of silicone basedcompositions used as room temperature cure sealants, to includeadditives which serve to “extend” and/or “plasticise” the siliconesealant composition by blending the or each extending compound(henceforth referred to as an “processing aid”) and/or plasticisingcompound (henceforth referred to as a “plasticiser”) with thepre-prepared polymer and other ingredients of the composition.

A processing aid (sometimes also referred to as an extender or secondaryplasticiser) is used to dilute the sealant composition and basicallymake the sealant more economically competitive without substantiallynegatively affecting the properties of the sealant formulation. Theintroduction of one or more processing aids into a silicone sealantcomposition not only reduces the overall cost of the product but canalso affect the properties of resulting uncured and/or cured siliconesealants. The addition of processing aids can, to a degree, positivelyeffect the rheology, adhesion and clarity properties of a siliconesealant and can cause an increase in elongation at break and a reductionin hardness of the cured product both of which can significantly enhancethe lifetime of the cured sealant provided the processing aid is notlost from the cured sealant by, for example, evaporation or exudation.

A plasticiser (otherwise referred to as a primary plasticiser) is addedto a polymer composition to provide properties within the final polymerbased product to increase the flexibility and toughness of the finalpolymer composition. This is generally achieved by reduction of theglass transition temperature (T_(g)) of the cured polymer compositionthereby generally, in the case of sealants for example, enhancing theelasticity of the sealant which in turn enables movement capabilities ina joint formed by a silicone sealant with a significant decrease in thelikelihood of fracture of the bond formed between sealant and substratewhen a sealant is applied thereto and cured. Plasticisers are typicallyused to also reduce the modulus of the sealant formulation. Plasticisersmay reduce the overall unit cost of a sealant but that is not their mainintended use and indeed some plasticisers are expensive and couldincrease the unit cost of a sealant formulation in which they are used.Plasticisers tend to be generally less volatile than processing aids andare typically introduced into the polymer composition in the form ofliquids or low melting point solids (which become miscible liquidsduring processing. Typically, for silicone based compositionplasticisers are unreactive short chain siloxanes such aspolydimethylsiloxane having terminal triorganosiloxy groups wherein theorganic substituents are, for example, methyl, vinyl or phenyl orcombinations of these groups. Such polydimethylsiloxanes normally have aviscosity of from about 5 to about 100,000 mPa·s. Compatible organicplasticisers may additionally be used, examples include dialkylphthalates wherein the alkyl group may be linear and/or branched andcontains from six to 20 carbon atoms such as dioctyl, dihexyl, dinonyl,didecyl, diallanyl and other phthalates; adipate, azelate, oleate andsebacate esters, polyols such as ethylene glycol and its derivatives,organic phosphates such as tricresyl phosphate and/or triphenylphosphates, castor oil, tung oil, fatty acids and/or esters of fattyacids.

Processing aids need to be both sufficiently compatible with theremainder of the composition and as non-volatile as possible at thetemperature at which the resulting cured sealant is to be maintained(e.g. room temperature). However it has been found that whilst someproposed processing aids are effective during storage, at the time ofapplication of the sealant and at least for a time thereafter, there areseveral well known problems regarding their use. These include:—

-   (i) UV stability—the discolouring of cured sealants containing    processing aids upon prolonged exposure to UV light;-   (ii) Poor compatibility with the polymer composition (e.g. a sealant    composition) leading to their exuding from the sealant over time    which negatively effects the physical and aesthetic properties and    lifetime of the cured product e.g. sealant; and-   (iii) Staining of the surrounding substrates onto which the    processing aids exude from the composition.

The process used in the industry, for introducing processing aids and/orplasticisers into a polymer composition such as a sealant composition,consists of merely mixing all the pre-prepared ingredients, e.g.polymer, cross-linker, catalyst, filler and the or each processing aidand/or plasticiser together in appropriate amounts and orders ofaddition. Compatibility of organic processing aids and/or plasticiserswith the other ingredients in a silicone based polymer composition, is asignificantly greater problem than with respect to organic basedpolymers, silicone polymers into which the processing aids and/orplasticisers are introduced tend to be highly viscous polymers, and thechemical nature of the polymer being silicone based as opposed toorganic based can have significant effects on the compatibility. Thelevel of compatibility effectively determines the amount of processingaid and/or plasticiser which can be introduced into a polymercomposition. Typically this results in the introduction of significantlylower amounts of, in particular, processing aids into the compositionthan may be desired because the processing aid will not physically mixinto the polymer composition sufficiently well, particularly with thepre-formed polymer which is usually the largest component, other thanthe filler, in the composition. The problem of compatibility ofplasticisers and processing aids in silicone polymer compositions hasbeen known in the industry ever since the introduction of organicprocessing aids, which as far the inventors are aware, until the presentinvention has not been addressed other than by the proposal of an everincreasing number of organic based processing aids, each of which isphysically unable to be mixed into the sealant composition at amounts ofabout 30% by weight of the total amount of processing aid and polymer.

Historically, unreactive siloxanes such as trialkylsilyl terminatedpolydiorganosiloxanes (for example trimethylsilyl terminatedpolydimethyl siloxane (PDMS)) were originally used as processing aidsand/or plasticisers in silicone based sealants because they werechemically similar and had excellent compatibility.

A wide variety of organic compounds and compositions have been proposedfor use as processing aids for reducing the cost of the silicone sealantcompositions. These materials are generally classified into two groupsas high volatility processing aids and low volatility processing aids.

Compositions containing high volatility processing aids may contain e.g.toluene or xylene. The high volatility of these compounds causes anumber of disadvantages in sealant formulations including, highshrinkage (high volume loss due to evaporation of the solvent),flammability, VOC (volatile organic content), hazardous componentlabelling, health and safety issues, etc.

Low volatility processing aids (sometimes referred to as highermolecular weight processing aids), are chosen with the intention ofhaving good compatibility with the polymers in the sealant compositions.The resulting sealants are termed “extended sealants” and generally showmuch more acceptable properties than diluted sealants. These lowermolecular weight processing aids can completely or partially replace thePDMS plasticizer in the formulation.

Low molecular weight polyisobutylenes (PIB) are proposed as processingaids in DE 2364856 and DE 3217516, however, due to the limitedcompatibility, the maximum amount of PIB processing aid that can beadded to an acetoxy silicone sealant formulation is typically in the25-30% (by weight) range. A higher addition level causes the processingaid to bleed to the surface and makes the cured sealant surface sticky.Phosphate esters are described as potential processing aids in DE2802170 and DE 2653499.

Mineral oil fractions (e.g. isoparaffins) and polyalkylbenzenes such asheavy alkylates (alkylated aromatic materials remaining afterdistillation of oil in a refinery) have also been proposed as processingaids. These and other organic compounds and mixtures proposed asprocessing aid materials for silicone sealant compositions are describedin the following publications:—

-   GB2041955 describes the use of dodecyl benzene and other alkylarenes    as organic processing aids. GB2012789 describes the use of trioctyl    phosphate for the partial replacement of PDMS. DE3342026 and    DE3342027 describe the use of esters of aliphatic monocarboxylic    acids as processing aids. EP0043501 proposes the use of between 0.2    and 15% by weight of the sealant composition of branched and/or    cyclic paraffin hydrocarbons such as cyclohexane, isohexane and    isooctodecane. EP0801101 describes the use of a mixture of paraffin    oils (molecular weight >180) in combination with one or more alkyl    aromatic compounds. EP0842974 describes the use of alkylcyclohexanes    (molecular weight >220). WO99/66012 and WO 00/27910 describe oil    resistant silicone compositions containing one or more aliphatic    liquid polymers and oils, petroleum derived organic oils, alkyl    phosphates, polyalkylene glycol, poly (propylene oxides),    hydroxyethylated alkyl phenol, dialkyldithiophosphonate, poly    (isobutylenes), poly (a-olefins) and mixtures thereof as processing    aids.

In recent years the industry has increasingly used paraffinichydrocarbons as processing aids. EP0885921 describes the use ofparaffinic hydrocarbon mixtures containing 60 to 80% paraffinic and 20to 40% naphthenic and a maximum of 1% aromatic carbon atoms. EP 0807667appears to describe a similar processing aid comprising wholly orpartially of a paraffin oil comprising 36-40% cyclic paraffin oils and58 to 64% non-cyclic paraffin oils. WO99/65979 describes an oilresistant sealant composition comprising a plasticiser which may includeparaffinic or naphthenic oils and mixtures thereof amongst otherplasticisers. EP1481038 describes the use of a hydrocarbon fluidcontaining more than 60 wt. % naphthenics, at least 20 wt. % polycyclicnaphthenics and an ASTM D-86 boiling point of from 235 to 400° C.EP1252252 describes the use of an processing aid comprising ahydrocarbon fluid having greater than 40 parts by weight cyclicparaffinic hydrocarbons and less than 60 parts by weight monocyclicparaffinic hydrocarbons based on 100 parts by weight of hydrocarbons.EP1368426 describes a sealant composition for use with alkyd paintscontaining a liquid paraffinic hydrocarbon “processing aid” whichpreferably contains greater than 40% by weight of cyclic paraffins.

As mentioned above a fundamental problem with the use of extendingmaterials is their lack of compatibility with components in the uncuredsilicone sealant composition typically resulting in phase separationduring storage and exudation from the cured sealant over the completetemperature range of interest. It is commonly found that, after curing,sealants containing processing aids and/or plasticisers may exude saidprocessing aids and/or plasticisers resulting in a significant reductionin the lifetime of the cured sealant, a feature particularly prevalentwith processing aids having low boiling points, e.g. <100° C. Whilst itis in the interest of the manufacturer to incorporate a high loading ofprocessing aid into their sealant compositions, the physical mixing ofthe processing aid material with the other ingredients as advocated inall of the above documents is prevented through the lack ofcompatibility particularly with respect to high viscosity polymers wherethe viscous properties of the polymer component are a physical barrierto the incorporation of large volumes of processing aid into the sealantcompositions. It is generally found therefore that the amount ofprocessing aid, which may be incorporated into the sealant composition,is typically between 20 and 40% by weight dependent on the processingaid or combination of processing aids used.

Whilst many of the organic processing aids proposed above have potentialthey all generally have problems for example whilst alkylbenzeneprocessing aids have a seemingly suitable combination of properties,i.e. high boiling points, excellent compatibility with thepolydiorganosiloxane polymer matrix (resulting in cured siliconesealants of good to excellent transparency), low environmental impact,low vapour pressure (and therefore low shrinkage), positive effect onthe rheological properties (reduced stringing). However, when exposed toartificial or natural weathering, alkyl benzene extended sealants tendto yellow rather rapidly. After prolonged weathering, these extendedsealants continue to yellow, and also lose their transparency. Thisproblem does not occur with other processing aids, such as phosphateesters or polyisobutylene.

Furthermore, whilst the use of polymers with very high degrees ofpolymerisation in siloxane formulations, can result in severaladvantageous properties such as high elasticity the viscosity of suchpolymers is generally so great (i.e. silicone gums) that they becomeeither completely unmanageable with respect to inter-mixing with otheringredients, such as fillers, cross-linkers, processing aids and/orplasticisers, or require very high shear mixers which are expensive tooperate. There has therefore been a long-felt need within the industryto develop a process for the ease of introduction of silicone basedpolymers of very high degrees of polymerisation into compositions whilstavoiding the need for high cost equipment.

The inventors have now surprisingly developed a new process for thechain extension of a polymer comprising an at least partiallyorganopolysiloxane containing backbone involving the incorporation ofdiluents comprising processing aids and/or plasticisers in thepreparation of polymers by chain extension whilst avoiding compoundingproblems usually encountered with polymers of such viscosities. Suchdiluted polymers resulting from the above may provide productscomprising such polymers with new and advantageous properties incomparison with prior art materials.

In accordance with the present invention there is provided a method ofmaking a diluted chain extended organopolysiloxane containing polymercomprising the steps of:—

-   (a) reacting a pre-formed polymer with a chain extender reactable    with terminal groups of the polymer, said chain extender being    selected from the group of    -   (i) a Diacetamidosilane, a diacetoxysilane, a dichlorosilane, a        diaminosilane where each amino group has one or two N—H bonds        per nitrogen; a dialkoxysilane, a diamidosilane, a        hexaorganodisilazane, a diketoximinosilane;    -   (ii) a polydialkylsiloxane having a degree of polymerisation of        from 2 to 25 and having at least two acetamido or acetoxy or        amino or alkoxy or amido or ketoximo substituents per molecule,    -   (iii) an α-aminoalkyldialkoxyalkylsilane wherein the alkyl and        alkoxy groups contain from 1 to 6 carbon atoms,    -   (iv) a compound of the structure ZMe₂SiO(Me₂SiO)_(y)SiMe₂Z or        ZMe₂Si—Y—SiMe₂Z where Z is a heterocyclic Si—N group Y is a        divalent hydrocarbon radical selected from the group consisting        of —(CR₂)m- or —C₆H₄—, y is 0 or a whole number, and m is 2 to 6        inclusive and R is a monovalent hydrocarbon group;    -   (v) a dialkenylsilane, a dihydrosilane,    -   (vi) a polydialkylsiloxane having a degree of polymerisation of        from 2 to 25 and at least one Si-alkenyl bond per terminal        group,    -   (vii) a polydialkylsiloxane having a degree of polymerisation of        from 2 to 25 and at least one Si—H bond per terminal group;        in the presence of a diluent material, a suitable catalyst and        optionally an end-blocking agent; and-   (b) where required quenching the chain extension process;    -   wherein the diluent material is substantially retained within        the resulting diluted organopolysiloxane containing polymer.

In accordance with the present invention there is provided a dilutedchain extended organopolysiloxane containing polymer obtainable by amethod comprising the steps of:—

-   (a) reacting a pre-formed organopolysiloxane containing polymer with    a chain extender reactable with terminal groups of said polymer,    said chain extender being selected from the group of    -   (i) a Diacetamidosilane, a diacetoxysilane, a diaminosilane        where each amino group has one or two N—H bonds per nitrogen; a        dialkoxysilane, a diamidosilane, a hexaorganodisilazane, a        diketoximinosilane;    -   (ii) a polydialkylsiloxane having a degree of polymerisation of        from 2 to 25 and having at least two acetamido or acetoxy or        amino or alkoxy or amido or ketoximo substituents per molecule,    -   (iii) an α-aminoalkyldialkoxyalkylsilane wherein the alkyl and        alkoxy groups contain from 1 to 6 carbon atoms,    -   (iv) a compound of the structure ZMe₂SiO(Me₂SiO)_(y)SiMe₂Z or        ZMe₂Si—Y—SiMe₂Z where Z is a heterocyclic Si—N group Y is a        divalent hydrocarbon radical selected from the group consisting        of —(CR₂)m- or —C₆H₄—, y is 0 or a whole number, and m is 2 to 6        inclusive and R is a monovalent hydrocarbon group;    -   (v) a dialkenylsilane, a dihydrosilane,    -   (vi) a polydialkylsiloxane having a degree of polymerisation of        from 2 to 25 and at least one Si-alkenyl bond per terminal        group,    -   (vii) a polydialkylsiloxane having a degree of polymerisation of        from 2 to 25 and at least one Si—H bond per terminal group;        in the presence of a diluent material, a suitable catalyst and        optionally an end-blocking agent; and-   (b) where required quenching the chain extension process;    -   wherein the diluent material is substantially retained within        the resulting diluted organopolysiloxane containing polymer.

The concept of “comprising” where used herein is used in its widestsense to mean and to encompass the notions of “include” and “consistof”. An organosiloxane containing polymer is intended to mean a polymercomprising multiple organopolysiloxane units per molecule and isintended to include a polymer substantially containing onlyorganopolysiloxane groups in the polymer chain or polymers where thebackbone contains both organopolysiloxane groups and e.g. organicpolymeric groups in the chain. Unless otherwise indicated all viscosityvalues given are at a temperature of 25° C. For the purpose of thisapplication “Substituted” means one or more hydrogen atoms in ahydrocarbon group has been replaced with another substituent. Examplesof such substituents include, but are not limited to, halogen atoms suchas chlorine, fluorine, bromine, and iodine; halogen atom containinggroups such as chloromethyl, perfluorobutyl, trifluoroethyl, andnonafluorohexyl; oxygen atoms; oxygen atom containing groups such as(meth)acrylic and carboxyl; nitrogen atoms; nitrogen atom containinggroups such as amino-functional groups, amido-functional groups, andcyano-functional groups; sulphur atoms; and sulphur atom containinggroups such as mercapto groups.

Preferably the diluents are miscible or at least substantially misciblewith the polymeric starting materials with which they are initiallymixed, and more particularly with both intermediate reaction productsand the final chain extended polymer product. The term “Substantiallymiscible diluents” is intended to include diluents which are completelyor largely miscible with the monomer and/or oligomer and/or the reactionmixture during polymerisation and hence may include low melting pointsolids which become miscible liquids in a reaction mixture during thepolymerisation process.

In one embodiment of the present invention the pre-formed polymercomponent used in the present invention is a polysiloxane containingpolymer containing at least two condensable groups, most preferably thecondensable groups are terminal hydroxyl or hydrolysable groups.Preferably the polymer has the general formulaX¹-A-X²  (1)where X¹ and X² are independently selected from silyl groups whichcontain in hydroxyl or hydrolysable groups and A is selected from asiloxane containing polymeric or copolymeric molecular chain or asiloxane/organic block copolymeric molecular chain. Examples of X¹ or X²groups incorporating hydroxyl and/or hydrolysable substituents include—SiOH₃, —(R^(a))SiOH₂, —(R^(a))₂SiOH, —R^(a)Si(OR^(b))₂, —Si(OR^(b))₃,—R^(a) ₂SiOR^(b) or —R^(a) ₂Si—R^(c)—SiR^(d) _(p)(OR^(b))_(3-p) whereeach R^(a) independently represents a monovalent hydrocarbyl group, forexample, an alkyl group, in particular having from 1 to 8 carbon atoms,(and is preferably methyl); each R^(b) and R^(d) group is independentlyan alkyl or alkoxy group in which the alkyl groups suitably have up to 6carbon atoms; R^(c) is a divalent hydrocarbon group which may beinterrupted by one or more siloxane spacers having up to six siliconatoms; and p has the value 0, 1 or 2.

Alternatively X¹ and X² may both comprise a group which will undergo anaddition type reaction with a suitable chain extending molecule.Preferably the addition type reaction is a hydrosilylation reaction andX and X¹ both contain either a silicon-hydrogen bond or unsaturatedorganic groups containing from 2 to 6 carbon atoms such as alkenylgroups, alkynyl groups, acrylate groups and/or alkylacrylate groups.Most preferably in this embodiment X¹ and X² are alkenyl groups withvinyl groups being particularly preferred. A small proportion (<20%) ofX¹ groups may comprise trialkylsilyl groups, in which each alkyl groupis preferably methyl or ethyl.

Examples of suitable siloxane groups A in formula (I) are those whichcomprise a polydiorganosiloxane chain. Thus group A preferably includessiloxane units of formula (2)(R⁵ _(s)SiO_((4-s)/2))—  (2)in which each R⁵ is independently an organic group such as a hydrocarbongroup having from 1 to 18 carbon atoms, a substituted hydrocarbon grouphaving from 1 to 18 carbon atoms or a hydrocarbonoxy group having up to18 carbon atoms and a has, on average, a value of from 1 to 3,preferably 1.8 to 2.2. Preferably R⁵ is a hydrocarbyl group having from1 to 10 carbon atoms optionally substituted with one or more halogengroup such as chlorine or fluorine and s is 0, 1 or 2. Particularexamples of groups R⁵ include methyl, ethyl, propyl, butyl, vinyl,cyclohexyl, phenyl, tolyl group, a propyl group substituted withchlorine or fluorine such as 3,3,3-trifluoropropyl, chlorophenyl,beta-(perfluorobutyl)ethyl or chlorocyclohexyl group. Suitably, at leastsome and preferably substantially all of the groups R⁵ are methyl.

Group A in the compound of formula (1) may include any suitable siloxaneor siloxane/organic molecular chain providing the resulting polymer aviscosity (in the absence of diluents in accordance with the presentinvention of up to 20 000 000 mPa·s, at 25° C. (i.e. up to or even morethan 200 000 units of formula (2)). In one preferred embodiment A is alinear organopolysiloxane molecular chain (i.e. s=2) for all chainunits. Preferred materials have polydiorganosiloxane chains according tothe general formula (3)—(R⁵ ₂SiO)_(t)—  (3)in which each R⁵ is as defined above and is preferably a methyl groupand t has a value of up to at least 200 000. Suitable polymers haveviscosities of up to 20 000 000 mPa·s at 25° C. in the absence of thediluent(s) but when prepared in the presence of the diluent(s)viscosities are generally in the order of 1000 to 100 000 mPa·s at 25°C. because of the presence of the diluent(s) in the polymer matrix.

Preferred polysiloxanes containing units of formula (2) are thuspolydiorganosiloxanes having terminal, silicon-bound hydroxyl groups orterminal, silicon-bound organic radicals which can be hydrolysed usingmoisture as defined as X¹ and X² above. The polydiorganosiloxanescomprising units of the structure in structure (2) may be homopolymersor copolymers. Mixtures of different polydiorganosiloxanes havingterminal condensable groups are also suitable.

In the case of polydiorganosiloxane co-polymers the polymeric chain maycomprise blocks made from chains of units depicted in figure (2) abovewhere the two R⁵ groups are:—

-   -   both alkyl groups (preferably both methyl or ethyl), or    -   alkyl and phenyl groups, or    -   alkyl and fluoropropyl, or    -   alkyl and vinyl or    -   alkyl and hydrogen groups.        Typically at least one block will comprise siloxane units in        which both R⁵ groups are alkyl groups.

Whilst preferably A is an organopolysiloxane molecular chain, A mayalternatively be a block copolymeric backbone comprising at least oneblock of siloxane groups of the type depicted in formula (2) above andan organic component comprising any suitable organic based polymerbackbone for example the organic polymer backbone may comprise, forexample, polystyrene and/or substituted polystyrenes such aspoly(α-methylstyrene), poly(vinylmethylstyrene), dienes, poly(p-trimethylsilylstyrene) and poly(p-trimethylsilyl-α-methylstyrene). Otherorganic components which may be incorporated in the polymeric backbonemay include acetylene terminated oligophenylenes, vinylbenzyl terminatedaromatic polysulphones oligomers, aromatic polyesters, aromaticpolyester based monomers, polyalkylenes, polyurethanes, aliphaticpolyesters, aliphatic polyamides and aromatic polyamides and the like.

However perhaps the most preferred organic based polymeric blocks in Aare polyoxyalkylene based blocks, which typically bond with siloxanesvia a hydrosilylation reaction prior to introduction of the chainextender of the present invention. Such polyoxyalkylene blockspreferably comprise a linear predominantly oxyalkylene polymer comprisedof recurring oxyalkylene units, (—C_(n)H_(2n)—O—) illustrated by theaverage formula (—C_(n)H_(2n)—O—)_(y) wherein n is an integer from 2 to4 inclusive and y is an integer of at least four. The number averagemolecular weight of each polyoxyalkylene polymer block may range fromabout 300 to about 10,000. Moreover, the oxyalkylene units are notnecessarily identical throughout the polyoxyalkylene monomer, but candiffer from unit to unit. A polyoxyalkylene block, for example, can becomprised of oxyethylene units, (—C₂H₄—O—); oxypropylene units(—C₃H₆—O—); or oxybutylene units,

(—C₄H₈—O—); or mixtures thereof. Preferably the polyoxyalkylenepolymeric backbone consists essentially of oxyethylene units oroxypropylene units.

Other polyoxyalkylene blocks may include for example: units of thestructure—[—R^(e)—O—(—R^(f)—O—)_(h)-Pn-CR^(g) ₂-Pn-O—(—R^(f)—O—)_(q)—R^(e)]—in which Pn is a 1,4-phenylene group, each R^(e) is the same ordifferent and is a divalent hydrocarbon group having 2 to 8 carbonatoms, each R^(f) is the same or different and, is, an ethylene group orpropylene group, each R^(g) is the same or different and is a hydrogenatom or methyl group and each of the subscripts h and q is a positiveinteger in the range from 3 to 30.

Any suitable method for making the polymer in accordance with the methodof the present invention may be used. The diluent, chain extender andcatalyst may be added in any order to the polymer. In one preferredoption the chain extender and catalyst are initially mixed with thepolymer and the chain extension reaction is commenced with the diluentadded once an increase in the viscosity of the reaction mixture has beendetected. Mixing is continued until the viscosity of the resultingproduct becomes constant or starts to decrease with time at which point,if required, the catalyst is quenched/neutralised.

An end-blocking agent may be used to regulate the molecular weight ofthe polymer and/or to add functionality. End-blocking agents are a meansof controlling the reactivity/polymer chain length of the polymer and asa means of introducing functionality to the resulting polymer. Suitableend-blockers are, for example, polysiloxanes in the number averagemolecular weight range from 160 upwards, in particularpolydimethylsiloxanes having one or more functional groups such ashydroxy, vinyl or hydrogen. Functional groups introduced usingend-blocking agents include alternative end groups on the polymer, e.g.silicon bonded hydrogen groups, alkenyl groups hydrolysable group suchas hydroxy groups, alkoxy groups and acetoxy groups. Hydrolysable groupswhich may be introduced using end-blockers and where required subsequentreactions include —SiOH₃, —(R^(a))SiOH₂, —(R^(a))₂SiOH,—R^(a)Si(OR^(b))₂, —Si(OR^(b))₃, —R^(a) ₂SiOR^(b) or —R^(a)₂Si—R^(c)—SiR^(d) _(p)(OR^(b))_(3-p) where each R^(a), R^(b), R^(d),R^(c) p are as hereinbefore described. Water also acts as a end-blocker,with the introduction of hydroxy functional groups.

Preferably the or each diluent is/are one or more processing aids and/orplasticisers. Generally the diluent(s) used in accordance with thepresent invention are not intended to chemically bond to themonomer/oligomer starting materials or intermediate or finalpolymerisation product. However, some chemical bonding and/or reversibleinteractions between the polymer reaction products and diluent(s) mayoccur, preferably between the diluent(s) and substituents along thebackbone of the polymer rather than with polymer end groups so as toform a cross-linking network between polymer and diluent therebyproviding a polymer product which is less likely to result in diluentloss and/or shrinkage when used in for example a sealant composition.For the sake of clarification with respect to this paragraph the term“chemically bond” is intended to mean the formation of covalent or thelike bonds and not mere chemical interactions such as hydrogen bondingor the like.

Any suitable processing aids and/or plasticiser or combination ofprocessing aids and/or plasticisers may be utilised. These include eachof the following alone or in combination with others from the list:—

-   trialkylsilyl terminated polydialkyl siloxane where each alkyl group    may be the same or different and comprises from 1 to 6 carbon atoms    but is preferably a methyl group, preferably with a viscosity of    from 100 to 100 000 mPa·s at 25° C. and most preferably from 1000 to    60 000 mPa·s at 25° C.;

polyisobutylenes (PIB),

phosphate esters such as trioctyl phosphate

polyalkylbenzenes,

-   linear and/or branched alkylbenzenes such as heavy alkylates,    dodecyl benzene and other alkylarenes,-   esters of aliphatic monocarboxylic acids;-   dialkyl phthalates wherein the alkyl group may be linear and/or    branched and contains from six to 20 carbon atoms such as dioctyl,    dihexyl, dinonyl, didecyl, diallanyl and other phthalates;-   adipate, azelate, oleate and sebacate esters,-   tung oil,-   fatty acids and/or esters of fatty acids.-   polyols such as ethylene glycol and its derivatives,-   organic phosphates such as tricresyl phosphate and/or triphenyl    phosphates and/or castor oil.-   linear or branched mono unsaturated hydrocarbons such as linear or    branched alkenes or mixtures thereof containing from 12 to 25 carbon    atoms; and/or-   mineral oil fractions comprising linear (e.g. n-paraffinic) mineral    oils, branched (iso-paraffinic) mineral oils, cyclic (referred in    some prior art as naphthenic) mineral oils and mixtures thereof. Any    suitable compatable mineral oil may be used, examples include linear    or branched mono unsaturated hydrocarbons such as linear or branched    alkenes or mixtures thereof containing at least 12, e.g. from 12 to    25 carbon atoms; and/or mineral oil fractions comprising linear    (e.g. n-paraffinic) mineral oils, branched (iso-paraffinic) mineral    oils, cyclic (referred in some prior art as naphthenic) mineral oils    and mixtures thereof. Preferably the hydrocarbons utilised comprise    at least 10, preferably at least 12 and most preferably greater than    20 carbon atoms per molecule.

Preferred processing aids include the mineral oil fractions,alkylcycloaliphatic compounds and alkybenzenes includingpolyalkylbenzenes and for some applications polydialkylsiloxanes withterminal groups which are unreactive with the polymer. Such compoundsmay be utilised in the present invention where appropriate butpreferably those used have an initial boiling point of greater than 200°C. (ASTM D-86).

Any suitable mixture of mineral oil fractions may be utilised as theextender in the present invention but high molecular weight extenders(e.g. >number average molecular weight of 220) are particularlypreferred. Examples include:—

-   alkylcyclohexanes (molecular weight >220);-   paraffinic hydrocarbons and mixtures thereof containing from 1 to    99%, preferably from 15 to 80% n-paraffinic and/or isoparaffinic    hydrocarbons (linear branched paraffinic) and 1 to 99%, preferably    85 to 20% cyclic hydrocarbons (naphthenic) and a maximum of 3%,    preferably a maximum of 1% aromatic carbon atoms. The cyclic    paraffinic hydrocarbons (naphthenics) may contain cyclic and/or    polycyclic hydrocarbons. Any suitable mixture of mineral oil    fractions may be used, e.g. mixtures containing-   (i) 60 to 80% paraffinic and 20 to 40% naphthenic and a maximum of    1% aromatic carbon atoms;-   (ii) 30-50%, preferably 35 to 45% naphthenic and 70 to 50%    paraffinic and or isoparaffinic oils;-   (iii) hydrocarbon fluids containing more than 60 wt. % naphthenics,    at least 20 wt. % polycyclic naphthenics and an ASTM D-86 boiling    point of greater than 235° C.;-   (iv) hydrocarbon fluid having greater than 40 parts by weight    naphthenic hydrocarbons and less than 60 parts by weight paraffinic    and/or ispoaraffinic hydrocarbons based on 100 parts by weight of    hydrocarbons.

Preferably the mineral oil based extender or mixture thereof comprisesat least one of the following parameters:—

-   -   (i) a molecular weight of greater than 150, most preferably        greater than 200;    -   (ii) an initial boiling point equal to or greater than 230° C.        (according to ASTM D 86).    -   (iii) a viscosity density constant value of less than or equal        to 0.9; (according to ASTM 2501)    -   (iv) an average of at least 12 carbon atoms per molecule, most        preferably 12 to 30 carbon atoms per molecule;    -   (v) an aniline point equal to or greater than 70° C., most        preferably the aniline point is from 80 to 110° C. (according to        ASTM D 611);    -   (vi) a naphthenic content of from 20 to 70% by weight of the        extender and a mineral oil based extender has a paraffinic        content of from 30 to 80% by weight of the extender according to        ASTM D 3238);    -   (vii) a pour point of from −50 to 60° C. (according to ASTM D        97);    -   (viii) a kinematic viscosity of from 1 to 20 cSt at 40° C.        (according to ASTM D 445)    -   (ix) a specific gravity of from 0.7 to 1.1 (according to ASTM        D1298);    -   (x) a refractive index of from 1.1 to 1.8 at 20° C. (according        to ASTM D 1218)    -   (xi) a density at 15° C. of greater than 700 kg/m³(according to        ASTM D4052) and/or    -   (xii) a flash point of greater than 100° C., more preferably        greater than 110° C. (according to ASTM D 93)    -   (xiii) a saybolt colour of at least +30 (according to ASTM D        156)    -   (xiv) a water content of less than or equal to 250 ppm        (according to ASTM D6304)    -   (xv) a Sulphur content of less than 2.5 ppm (according to ASTM D        4927)

The alkylbenzene compounds suitable for use include heavy alkylatealkylbenzene or an alkylcycloaliphatic compound. Examples of alkylsubstituted aryl compounds useful as processing aids and/or plasticisersare compounds which have aryl groups, especially benzene substituted byalkyl and possibly other substituents, and a molecular weight of atleast 200. Examples of such processing aids are described in U.S. Pat.No. 4,312,801, the content of which is incorporated herein by reference.These compounds can be represented by general formula (I), (II), (III)and (IV)

where R⁶ is an alkyl chain of from 1 to 30 carbon atoms, each of R⁷through to R¹⁶ is independently selected from hydrogen, alkyl, alkenyl,alkynyl, halogen, haloalkyl, nitrile, amine, amide, an ether such as analkyl ether or an ester such as an alkyl ester group, and n is aninteger of from 1 to 25.

In particular, the processing aid used in accordance with the process ofthe present invention is of formula (I) where each of R⁷, R⁸, R⁹, R¹⁰and R¹¹ is hydrogen and R⁶ is a C₁₀-C₁₃ alkyl group. A particularlyuseful source of such compounds are the so-called “heavy alkylates”,which are recoverable from oil refineries after oil distillation.Generally distillation takes place at temperatures in the range of from230-330° C., and the heavy alkylates are present in the fractionremaining after the lighter fractions have been distilled off.

Examples of alkylcycloaliphatic compounds are substituted cyclohexaneswith a molecular weight in excess of 220. Examples of such compounds aredescribed in EP 0842974, the content of which is incorporated herein byreference. Such compounds may be represented by general formula (V).

where R¹⁷ is a straight or branched alkyl group of from 1 to 25 carbonatoms, and R¹⁸ and R¹⁹ are independently selected from hydrogen or aC₁₋₂₅ straight or branched chain alkyl group.

The amount of diluent which may be included in the composition willdepend upon factors such as the purpose to which the composition is tobe put, the molecular weight of the diluent(s) concerned etc. Polymerproducts in accordance with the present invention may contain from 5%w/w up to 70% w/w diluent (based on the combined weight of polymer anddiluent(s)) depending upon these factors. In general however, the higherthe molecular weight of the diluent(s), the less will be tolerated inthe composition. Typical compositions will contain up to 70% w/wdiluent(s). More suitable polymer products comprise from 30-60% w/w of alinear diluent(s) whereas 25-35% w/w will be more preferred when thediluent is a heavy alkylate.

The chain extender may be any suitable molecule as hereinbeforedescribed which will react with the polymer to generate a reactionproduct with a greater polymer chain length (i.e. dp and molecularweight). Preferably the chain extender is a silane or short chainsiloxane (i.e. having an average chain length of from 2 to about 25)with two reactive end groups designed to react with the terminal groupsof the pre-formed polymer.

For pre-formed polymers with hydroxy or otherwise condensable end groupssuitable chain extender include for example:—

-   Diacetamidosilanes such as dialkyldiacetamidosilanes or    alkenylalkyldiacetamidosilanes, particularly    methylvinyldi(N-methylacetamido)silane, or    dimethyldi(N-methylacetamido)silane diacetoxysilanes, such as    dialkyldiacetoxysilanes and alkylalkenyldiacetoxysilanes    diaminosilanes, such as dialkyldiaminosilanes or    alkylalkenyldiaminosilanes particularly those where each amino group    has one Si—N bond and two N—C bonds;-   dialkoxysilanes such as dimethoxydimethylsilane and    diethoxydimethylsilane;-   a polydialkylsiloxane having a degree of polymerisation of from 2 to    25 and having at least two acetamido or acetoxy or amino or alkoxy    or amido or ketoximo substituents per molecule, wherein each alkyl    group independently comprises from 1 to 6 carbon atoms;-   hexaorganocyclotrisilazanes, octoorganocyclotetrasilazanes,    diamidosilanes such as dialkyldiamidosilanes or    alkylalkenyldiamidosilanes diketoximinosilanes such as    dialkylkdiketoximinosilanes and alkylalkenyldiketoximinosilanes    α-aminoalkyldialkoxyalkylsilanes wherein the alkyl and alkoxy groups    contain from 1 to 5 carbon atoms, such as    α-aminomethyldialkoxymethylsilanes particularly preferred are those    where aminomethyl group is an N,N-dialkylaminomethyl group and chain    extenders in the form of silicon compounds having the formula    ZMe₂SiO(Me₂SiO)_(y)SiMe₂Z or ZMe₂Si—Y—SiMe₂Z    where Z, Y, y and m are as hereinbefore described.

Specific examples of chain extenders include alkenyl alkyldialkoxysilanes such as vinyl methyl dimethoxysilane, vinylethyldimethoxysilane, vinyl methyldiethoxysilane,vinylethyldiethoxysilane, alkenylalkyldioximosilanes such as vinylmethyl dioximosilane, vinyl ethyldioximosilane, vinylmethyldioximosilane, vinylethyldioximosilane,alkenylalkyldiacetoxysilanes such as vinyl methyl diacetoxysilane, vinylethyldiacetoxysilane, and alkenylalkyldihydroxysilanes such as vinylmethyl dihydroxysilane, vinyl ethyldihydroxysilane, vinylmethyldihydroxysilane,vinylethyldihydroxysilane.methylphenyl-dimethoxysilane, di-butoxydiacetoxysilane, Alkylalkenylbis(N-alkylacetamido) silanes such asmethylvinyldi-(N-methylacetamido)silane andmethylvinyldi-(N-ethylacetamido)silane; dialkylbis(N-arylacetamido)silanes such as dimethyldi-(N-methylacetamido)silane; anddimethyldi-(N-ethylacetamido)silane; Alkylalkenylbis(N-arylacetamido)silanes such as methylvinyldi(N-phenylacetamido)silane anddialkylbis(N-arylacetamido) silanes such asdimethyldi-(N-phenylacetamido)silane, methylvinylbis(N-methylacetamido)silane, methylhydrogendiacetoxysilane,dimethylbis(N-diethylaminoxy)silane anddimethylbis(sec.-butylamino)silane. The chain extender used may alsocomprise any combination of two or more of the above.

For pre-formed polymers with alkenyl or Si—H end groups suitable foraddition reactions via a hydrosilylation route chain extender includefor example:—

-   A silane comprising two alkenyl groups, a dihydrosilane, a    polydialkylsiloxane having a degree of polymerisation of from 2 to    25 and at least one Si-alkenyl bond per terminal group,-   A polydialkylsiloxane having a degree of polymerisation of from 2 to    25 and at least one Si—H bond per terminal group and wherein each    alkyl group independently comprises from 1 to 6 carbon atoms;-   organosilicon compounds with the general formula

in which R is as hereinbefore described, j is 1, 2, or 3, k is 0 or 1,and j+Fk is 2 or 3.

exemplified by compounds with the following formulas,(ViMe₂SiO)₂SiVi(OMe)₁(ViMe₂SiO)₁SiVi(OMe)₂,(ViMe₂SiO)₂SiVi(OEt)_(1′)(ViMe₂SiO)₁SiVi(OEt)₂,(ViMe₂SiO)₃Si(OMe)₁(ViMe₂SiO)₂Si(OMe)₂, (ViMe₂SiO)₃Si(OEt)₁ and(ViMe₂SiO)₂Si(OEt)₂

As used herein, Vi represents a vinyl group, Me represents a methylgroup, and Et represents an ethyl group.

The catalyst used to catalyse the chain extension reaction is determinedby the reaction to take place. The composition further comprises acondensation catalyst. In the case where the reaction involved in chainextension is a condensation reaction, any suitable condensation catalystmay be utilised to chain extend the polymer composition including tin,lead, antimony, iron, cadmium, barium, manganese, zinc, chromium,cobalt, nickel, titanium, aluminium, gallium or germanium and zirconiumbased catalysts such as organic tin metal catalysts and 2-ethylhexoatesof iron, cobalt, manganese, lead and zinc may alternatively be used.Organotin, titanate and/or zirconate based catalysts are preferred.

Chain extension reactions which contain oximosilanes or acetoxysilanesgenerally use a tin catalyst for curing, such as triethyltin tartrate,tin octoate, tin oleate, tin naphthate, butyltintri-2-ethylhexoate,tinbutyrate, carbomethoxyphenyl tin trisuberate, isobutyltintriceroate,and diorganotin salts especially diorganotin dicarboxylate compoundssuch as dibutyltin dilaurate, dimethyltin dibutyrate, dibutyltindimethoxide, dibutyltin diacetate, dimethyltin bisneodecanoateDibutyltin dibenzoate, stannous octoate, dimethyltin dineodeconoate,dibutyltin dioctoate. Dibutyltin dilaurate, dibutyltin diacetate areparticularly preferred.

For compositions which include alkoxysilane based chain extendercompounds, the preferred catalysts are titanate or zirconate compounds.Such titanates may comprise a compound according to the general formulaTi[OR²¹]₄ where each R²¹ may be the same or different and represents amonovalent, primary, secondary or tertiary aliphatic hydrocarbon groupwhich may be linear or branched containing from 1 to 10 carbon atoms.Optionally the titanate may contain partially unsaturated groups.However, preferred examples of R²¹ include but are not restricted tomethyl, ethyl, propyl, isopropyl, butyl, tertiary butyl and a branchedsecondary alkyl group such as 2,4-dimethyl-3-pentyl. Preferably, wheneach R²¹ is the same, R²¹ is an isopropyl, branched secondary alkylgroup or a tertiary alkyl group, in particular, tertiary butyl.

Examples include tetrabutyltitanate, tetraisopropyltitanate, or chelatedtitanates or zirconates (the chelation may be with any suitablechelating agent such as an alkyl acetylacetonate such as methyl orethylacetylacetonate) such as for example diisopropylbis(acetylacetonyl)titanate, diisopropylbis(ethylacetoacetonyl)titanate, diisopropoxytitaniumBis(Ethylacetoacetate) and the like. Further examples of suitablecatalysts are described in EP1254192 which is incorporated herein byreference. The amount of catalyst used depends on the cure system beingused but typically is from 0.01 to 3% by weight of the total composition

Preferably the catalyst, component (d), will be present in an amount offrom about 0.1 to 3 weight % of the composition component (d) may bepresent in a greater amount in cases where chelating agents are used.

In the case where the reaction between polymer and chain extender is anaddition reaction, the addition reaction is preferably a hydrosilylationreaction for which the catalyst chosen may comprise any suitablehydrosilylation catalyst such as a platinum group metal based catalystselected from a platinum, rhodium, iridium, palladium or rutheniumcatalyst. Platinum group metal containing catalysts useful to catalysecuring of the present compositions can be any of those known to catalysereactions of silicon bonded hydrogen atoms with silicon bonded alkenylgroups. The preferred platinum group metal for use as a catalyst toeffect cure of the present compositions by hydrosilylation is a platinumbased catalyst. Some preferred platinum based hydrosilylation catalystsfor curing the present composition are platinum metal, platinumcompounds and platinum complexes. Representative platinum compoundsinclude chloroplatinic acid, chloroplatinic acid hexahydrate, platinumdichloride, and complexes of such compounds containing low molecularweight vinyl containing organosiloxanes. Other hydrosilylation catalystssuitable for use in the present invention include for example rhodiumcatalysts such as [Rh(O₂CCH₃)₂]₂, Rh(O₂CCH₃)₃, Rh₂(C₈H₁₅O₂)₄,Rh(C₅H₇O₂)₃, Rh(C₅H₇O₂)(CO)₂, Rh(CO)[Ph₃P](C₅H₇O₂), RhX⁴ ₃[(R³)₂S]₃, (R²₃P)₂Rh(CO)X⁴, (R² ₃P)₂Rh(CO)H, Rh₂X⁴ ₂Y² ₄, H_(a)Rh_(b)olefin_(c)Cl_(d),Rh(O(CO)R³)_(3-n)(OH)_(n) where X⁴ is hydrogen, chlorine, bromine oriodine, Y is an alkyl group, such as methyl or ethyl, CO, C₈H₁₄ or 0.5C₈H₁₂, R³ is an alkyl radical, cycloalkyl radical or aryl radical and R²is an alkyl radical an aryl radical or an oxygen substituted radical, ais 0 or 1, b is 1 or 2, c is a whole number from 1 to 4 inclusive and dis 2, 3 or 4, n is 0 or 1. Any suitable iridium catalysts such asIr(OOCCH₃)₃, Ir(C₅H₇O₂)₃, [Ir(Z⁴)(En)₂]₂, or (Ir(Z⁴)(Dien)]₂, where Z⁴is chlorine, bromine, iodine, or alkoxy, En is an olefin and Dien iscyclooctadiene may also be used.

One of the most important aspects of the present invention is the factthat by polymerising the polymer in the presence of the diluent(s) theresulting polymer/processing aids and/or polymer/plasticiser mixthroughout the polymerisation process has a significantly lowerviscosity than would normally be expected because the viscosity reducingdiluent(s) is/are present in the polymer mixture as it polymerises. Itis to be understood that this is the case even when only a small amounte.g. 5-20% by weight is present for the polymerisation process inaccordance with the present invention. For example using the standardprocess of mixing diluent(s) with filler and ready made polymer togetherone would typically only be able to incorporate approximately 28% byweight of diluent(s) in an 80 000 mPa·s polymer because of problems withhandling and blending using polymers of greater viscosity. Byintroducing the diluent(s) prior to polymerisation, blending problemsare avoided and the resulting polymers may be utilised for alternativeapplications than are usually utilised using organopolysiloxane gums ofseveral million mPa·s.

The process of the present invention enables a significantly greateramount of diluent(s) to be used, in conjunction with polymers havingviscosities not previously contemplated because of handling problems.The ratio between the diluent(s) and the silicone phase that can beachieved is dependent on the miscibility of the diluent(s) in thepolydimethylsiloxanes and vice versa. The miscibility was found todepend at least in part, on the molecular weight of thepolydimethylsiloxanes.

This combination also provides the user with formulations comprising thediluted polymer of the present invention with a variety of improvedphysical characteristics, not least the elasticity of resultingproducts, because of the use of polymers having polymer chainlength/viscosities which hitherto would not have been possible to use.Applications include, sealants formulations, coating formulations, highconsistency organopolysiloxane gum formulations for high consistencyrubber applications, and for dispersions thereof alkylsilicone fluidsfor use in personal care products.

In accordance with the present invention there is provided a method ofmaking an a moisture curable composition capable of cure to anelastomeric body comprising the steps of:—

-   (i) Preparing a diluted chain extended organopolysiloxane containing    polymer as hereinbefore described using a condensable, preferably    hydroxy or otherwise hydrolysable group containing end-blocker-   (ii) compounding the resulting diluted organopolysiloxane polymer    with-   (iii) (i) a suitable cross-linking agent which is reactive with the    organopolysiloxane polymer,    -   (ii) a suitable condensation catalyst and optionally    -   (iii) filler.        Optionally a small proportion (<20%) of X¹ groups may comprise        trialkylsilyl groups, in which each alkyl group is preferably        methyl or ethyl.

In one embodiment the process is used to prepare a one or two partorganopolysiloxane sealant composition. A two part composition comprisesin the first part diluted polymer and filler (when required) and in thesecond part catalyst and cross-linker are provided for mixing in anappropriate ratio (e.g. from 1:1 to 10:1) immediately prior to use.Additional additives to be discussed below may be provided in eitherpart 1 or part 2 of the part composition but are preferably added inpart two.

In accordance with the present invention there is provided a moisturecurable composition capable of cure to an elastomeric body obtainable bya process comprising the steps of:—

-   -   (iv) Preparing a diluted chain extended organopolysiloxane        containing polymer as hereinbefore described using a        condensable, preferably hydroxy or otherwise hydrolysable group        containing end-blocker    -   (v) compounding the resulting diluted organopolysiloxane polymer        with

-   (vi) (i) a suitable cross-linking agent which is reactive with the    organopolysiloxane polymer,    -   (ii) a suitable condensation catalyst and optionally    -   (iii) filler.

In accordance with a still further embodiment of the present inventionthere is provided a moisture curable composition capable of cure to anelastomeric body, the composition comprising

-   a) A diluted chain extended organopolysiloxane containing polymer    having not less than two silicon-bonded condensable (preferably    hydroxyl or hydrolysable) groups obtainable as hereinbefore    described;-   b) A siloxane and/or silane cross-linker having at least two groups    per molecule which are reactable with the condensable groups in (a);-   c) Optionally one or more fillers and-   d) a suitable cure catalyst

Preferably the polymeric constituent of the diluted polymer inaccordance with the present invention has the general formulaX¹-A-X²  (1)Where A, X¹ and X² are as hereinbefore described. Preferably the polymerproduced in accordance with the present invention has an average numbermolecular weight (Mn) greater than 132,000 and a degree ofpolymerisation of greater than 1800 as determined by ASTM D5296-05 withthe weight values being determined in terms of polystyrene molecularweight equivalents.

Any suitable cross-linker may be used. The cross-linker used (b) in themoisture curable composition as hereinbefore described is preferably asilane compound containing hydrolysable groups. These include one ormore silanes or siloxanes which contain silicon bonded hydrolysablegroups such as acyloxy groups (for example, acetoxy, octanoyloxy, andbenzoyloxy groups); ketoximino groups (for example dimethyl ketoximo,and isobutylketoximino); alkoxy groups (for example methoxy, ethoxy, anpropoxy) and alkenyloxy groups (for example isopropenyloxy and1-ethyl-2-methylvinyloxy).

In the case of siloxane based cross-linkers the molecular structure canbe straight chained, branched, or cyclic.

The cross-linker may have two but preferably has three or foursilicon-bonded condensable (preferably hydrolysable) groups permolecule. When the cross-linker is a silane and when the silane hasthree silicon-bonded hydrolysable groups per molecule, the fourth groupis suitably a non-hydrolysable silicon-bonded organic group. Thesesilicon-bonded organic groups are suitably hydrocarbyl groups which areoptionally substituted by halogen such as fluorine and chlorine.Examples of such fourth groups include alkyl groups (for example methyl,ethyl, propyl, and butyl); cycloalkyl groups (for example cyclopentyland cyclohexyl); alkenyl groups (for example vinyl and allyl); arylgroups (for example phenyl, and tolyl); aralkyl groups (for example2-phenylethyl) and groups obtained by replacing all or part of thehydrogen in the preceding organic groups with halogen. Preferablyhowever, the fourth silicon-bonded organic groups is methyl.

Silanes and siloxanes which can be used as cross-linkers includealkyltrialkoxysilanes such as methyltrimethoxysilane (MTM) andmethyltriethoxysilane, alkenyltrialkoxy silanes such asvinyltrimethoxysilane and vinyltriethoxysilane, isobutyltrimethoxysilane(iBTM). Other suitable silanes include ethyltrimethoxysilane,vinyltriethoxysilane, phenyltrimethoxysilane, alkoxytrioximosilane,alkenyltrioximosilane, 3,3,3-trifluoropropyltrimethoxysilane,methyltriacetoxysilane, vinyltriacetoxysilane, ethyl triacetoxysilane,di-butoxy diacetoxysilane, phenyl-tripropionoxysilane,methyltris(methylethylketoximo)silane,vinyl-tris-methylethylketoximo)silane,methyltris(methylethylketoximino)silane, methyltris(isopropenoxy)silane,vinyltris(isopropenoxy)silane, ethylpolysilicate, n-propylorthosilicate,ethylorthosilicate, dimethyltetraacetoxydisiloxane. The cross-linkerused may also comprise any combination of two or more of the above.

The amount of cross-linker present in the composition will depend uponthe particular nature of the cross-linker and in particular, themolecular weight of the molecule selected. The compositions suitablycontain cross-linker in at least a stoichiometric amount as compared tothe polymeric material described above. Compositions may contain, forexample, from 2-30% w/w of cross-linker, but generally from 2 to 10%w/w. Acetoxy cross-linkers may typically be present in amounts of from 3to 8% w/w preferably 4 to 6% w/w whilst oximino cross-linkers, whichhave generally higher molecular weights will typically comprise from3-8% w/w.

The composition further comprises a condensation catalyst of the type ashereinbefore described in the chain extension of polymers having OH orcondensable end groups.

Compositions of this invention may contain, as optional constituents,other ingredients which are conventional to the formulation of siliconesealants and the like. For example, the compositions will normallycontain one or more finely divided, reinforcing fillers such as highsurface area fumed and precipitated silicas including rice hull ash andto a degree calcium carbonate, and/or one or more or additionalnon-reinforcing fillers such as crushed quartz, diatomaceous earths,barium sulphate, iron oxide, titanium dioxide and carbon black, talc,wollastonite. Other fillers which might be used alone or in addition tothe above include aluminite, calcium sulphate (anhydrite), gypsum,calcium sulphate, magnesium carbonate, clays such as kaolin, aluminiumtrihydroxide, magnesium hydroxide (brucite), graphite, copper carbonate,e.g. malachite, nickel carbonate, e.g. zarachite, barium carbonate, e.g.witherite and/or strontium carbonate e.g. strontianite.

Aluminium oxide, silicates from the group consisting of olivine group;garnet group; aluminosilicates; ring silicates; chain silicates; andsheet silicates. The olivine group comprises silicate minerals, such asbut not limited to, forsterite and Mg₂SiO₄. The garnet group comprisesground silicate minerals, such as but not limited to, pyrope;Mg₃Al₂Si₃O₁₂; grossular; and Ca₂Al₂Si₃O₁₂. Aluninosilicates compriseground silicate minerals, such as but not limited to, sillimanite;Al₂SiO₅; mullite; 3Al₂O₃.2SiO₂; kyanite; and Al₂SiO₅. The ring silicatesgroup comprises silicate minerals, such as but not limited to,cordierite and Al₃(Mg,Fe)₂[Si₄AlO₁₈]. The chain silicates groupcomprises ground silicate minerals, such as but not limited to,wollastonite and Ca[SiO₃].

The sheet silicates group comprises silicate minerals, such as but notlimited to, mica; K₂Al₁₄[Si₆Al₂O₂₀](OH)₄; pyrophyllite;Al₄[Si₈O₂₀](OH)₄; talc; Mg₆[Si₈O₂₀](OH)₄; serpentine for example,asbestos; Kaolinite; Al₄[Si₄O₁₀](OH)₈; and vermiculite.

In addition, a surface treatment of the filler(s) may be performed, forexample with a fatty acid or a fatty acid ester such as a stearate, orwith organosilanes, organosiloxanes, or organosilazanes hexaalkyldisilazane or short chain siloxane diols to render the filler(s)hydrophobic and therefore easier to handle and obtain a homogeneousmixture with the other sealant components. The surface treatment of thefillers makes the ground silicate minerals easily wetted by the siliconepolymer. These surface modified fillers do not clump, and can behomogeneously incorporated into the silicone polymer. This results inimproved room temperature mechanical properties of the uncuredcompositions. Furthermore, the surface treated fillers give a lowerconductivity than untreated or raw material.

The proportion of such fillers when employed will depend on theproperties desired in the elastomer-forming composition and the curedelastomer. Usually the filler content of the composition will residewithin the range from about 5 to about 800 parts by weight, preferably25 to 400 parts by weight per 100 parts by weight of the polymerexcluding the diluent portion.

Other ingredients which may be included in the compositions include butare not restricted to co-catalysts for accelerating the cure of thecomposition such as metal salts of carboxylic acids and amines;rheological modifiers; Adhesion promoters, pigments, Heat stabilizers,Flame retardants, UV stabilizers, Chain extenders, electrically and/orheat conductive fillers, cure modifiers, fungicides and/or biocides andthe like (which may suitably by present in an amount of from 0 to 8.0%by weight). It will be appreciated that some of the additives areincluded in more than one list of additives. Such additives would thenhave the ability to function in all the different ways referred to.Water scavengers e.g. isocyanates such as cyclohexylisocyanate,isophorone diisocyanate and hexamethylene diisocyanate, sometimesreferred to as deactivators may be incorporated in the composition butare preferably not utilised.

The rheological additives include silicone organic co-polymers such asthose described in EP 0802233 based on polyols of polyethers orpolyesters; non-ionic surfactants selected from the group consisting ofpolyethylene glycol, polypropylene glycol, ethoxylated castor oil, oleicacid ethoxylate, alkylphenol ethoxylates, copolymers or ethylene oxide(EO) and propylene oxide (PO), and silicone polyether copolymers; aswell as silicone glycols.

Any suitable adhesion promoter(s) may be incorporated in a sealantcomposition in accordance with the present invention. These may includefor example alkoxy silanes such as aminoalkylalkoxy silanes,epoxyalkylalkoxy silanes, for example, 3-glycidoxypropyltrimethoxysilaneand, mercapto-alkylalkoxy silanes and γ-aminopropyl triethoxysilane.Isocyanurates containing silicon groups such as1,3,5-tris(trialkoxysilylalkyl) isocyanurates may additionally be used.Further suitable adhesion promoters are reaction products ofepoxyalkylalkoxy silanes such as 3-glycidoxypropyltrimethoxysilane withamino-substituted alkoxysilanes such as 3-aminopropyltrimethoxysilaneand optionally alkylalkoxy silanes such as methyl-trimethoxysilaneepoxyalkylalkoxy silane, mercaptoalkylalkoxy silane, and derivativesthereof.

Heat stabilizers may include Iron oxides and carbon blacks, Ironcarboxylate salts, cerium hydrate, barium zirconate, titania, cerium andzirconium octoates, and porphyrins.

Flame retardants may include for example, carbon black, hydratedaluminium hydroxide, and silicates such as wollastonite, platinum andplatinum compounds.

Electrically conductive fillers may include carbon black, metalparticles such as silver particles any suitable, electrically conductivemetal oxide fillers such as titanium oxide powder whose surface has beentreated with tin and/or antimony, potassium titanate powder whosesurface has been treated with tin and/or antimony, tin oxide whosesurface has been treated with antimony, and zinc oxide whose surface hasbeen treated with aluminium.

Thermally conductive fillers may include metal particles such aspowders, flakes and colloidal silver, copper, nickel, platinum, goldaluminium and titanium, metal oxides, particularly aluminium oxide(Al₂O₃) and beryllium oxide (BeO); magnesium oxide, zinc oxide,zirconium oxide; Ceramic fillers such as tungsten monocarbide, siliconcarbide and aluminium nitride, boron nitride and diamond.

Any suitable Fungicides and biocides may be utilised, these includeN-substituted benzimidazole carbamate, benzimidazolylcarbamate such asmethyl 2-benzimidazolylcarbamate, ethyl 2-benzimidazolylcarbamate,isopropyl 2-benzimidazolylcarbamate, methylN-{2-[1-(N,N-dimethylcarbamoyl)benzimidazolyl]}carbamate, methylN-{2-[1-(N,N-dimethylcarbamoyl)-6-methylbenzimidazolyl]}carbamate,methylN-{2-[1-(N,N-dimethylcarbamoyl)-5-methylbenzimidazolyl]}carbamate,methyl N-{2-[1-(N-methylcarbamoyl)benzimidazolyl]}carbamate, methylN-{2-[1-(N-methylcarbamoyl)-6-methylbenzimidazolyl]}carbamate, methylN-{2-[1-(N-methylcarbamoyl)-5-methylbenzimidazolyl]}carbamate, ethylN-{2-[1-(N,N-dimethylcarbamoyl)benzimidazolyl]}carbamate, ethylN-{2-[2-(N-methylcarbamoyl)benzimidazolyl]}carbamate, ethylN-{2-[1-(N,N-dimethylcarbamoyl)-6-methylbenzimidazolyl]}carbamate, ethylN-{2-[1-(N-methylcarbamoyl)-6-methylbenzimidazolyl]}carbamate, isopropylN-{2-[1-(N,N-dimethylcarbamoyl)benzimidazolyl]}carbamate, isopropylN-{2-[1-(N-methylcarbamoyl)benzimidazolyl]}carbamate, methylN-{2-[1-(N-propylcarbamoyl)benzimidazolyl]}carbamate, methylN-{2-[1-(N-butylcarbamoyl)benzimidazolyl]}carbamate, methoxyethylN-{2-[1-(N-propylcarbamoyl)benzimidazolyl]}carbamate, methoxyethylN-{2-[1-(N-butylcarbamoyl)benzimidazolyl]}carbamate, ethoxyethylN-{2-[1-(N-propylcarbamoyl)benzimidazolyl]}carbamate, ethoxyethylN-{2-[1-(N-butylcarbamoyl)benzimidazolyl]}carbamate, methylN-{1-(N,N-dimethylcarbamoyloxy)benzimidazolyl]}carbamate, methylN-{2-[N-methylcarbamoyloxy)benzimidazolyl]}carbamate, methylN-{2-[1-(N-butylcarbamoyloxy)benzoimidazolyl]}carbamate, ethoxyethylN-{2-[1-(N-propylcarbamoyl)benzimidazolyl]}carbamate, ethoxyethylN-{2-[1-(N-butylcarbamoyloxy)benzoimidazolyl]}carbamate, methylN-{2-[1-(N,N-dimethylcarbamoyl)-6-chlorobenzimidazolyl]}carbamate, andmethyl N-{2-[1-(N,N-dimethylcarbamoyl)-6-nitrobenzimidazolyl]}carbamate.10,10′-oxybisphenoxarsine (trade name: Vinyzene, OBPA),di-iodomethyl-para-tolylsulfone,benzothiophene-2-cyclohexylcarboxamide-S,S-dioxide,N-(fluordichloridemethylthio)phthalimide (trade names: Fluor-Folper,Preventol A3). Methyl-benzimideazol-2-ylcarbamate (trade names:Carbendazim, Preventol BCM), Zinc-bis(2-pyridylthio-1-oxide) (zincpyrithion) 2-(4-thiazolyl)-benzimidazol, N-phenyl-iodpropargylcarbamate,N-octyl-4-isothiazolin-3-on,4,5-dichloride-2-n-octyl-4-isothiazolin-3-on,N-butyl-1,2-benzisothiazolin-3-on and/or Triazolyl-compounds, such astebuconazol in combination with zeolites containing silver.

The compositions are preferably room temperature vulcanisablecompositions in that they cure at room temperature without heating.

The compositions can be prepared by mixing the ingredients employing anysuitable mixing equipment. Other components may be added as necessary.For example preferred one part, moisture curable compositions may bemade by mixing together the extended polysiloxane having hydroxyl orhydrolysable groups and any organosilicon plasticizer or filler used,and mixing this with a pre-mix of the cross-linker and catalyst.UV-stabilisers pigments and other additives may be added to the mixtureat any desired stage.

After mixing, the compositions may be stored under substantiallyanhydrous conditions, for example in sealed containers, until requiredfor use.

The polymerisation in the presence of the diluent gives severaladvantages with respect to sealant formulations. In respect to rheology,the increase in polymer chain length enabled due to the presence of thediluent compensates for the amount of diluent present in the dilutedsealant and as such the viscosity of the diluted polymer issignificantly higher than it would be if the diluent had been added to astandard polymer used in sealant formulations currently having forexample a viscosity of 80000 to 100 000 mPa·s at 25 deg C. The lowermodulus of the resulting sealant additionally means that more movementis possible in the joint being sealed, to the extent that even ifdiluent loss occurs, the effective modulus caused by the presence ofhigh molecular weight polymers which may be prepared in accordance withthe process of the present invention is able to compensate for stresscaused to the seal due to shrinkage. The product of the process of thepresent invention gives superior processing advantages due to thecomparatively low viscosity of the diluted polymer when considering themolecular weight of the polymer.

Thus in a further aspect, the invention provides a method of sealing aspace between two units, said method comprising applying a compositionas described above and causing or allowing the composition to cure.Suitable units include glazing structures or building units as describedabove and these form a further aspect of the invention.

The applicants have found that sealant formulations according to thepresent invention provides the user with a very highly elastic sealantsubsequent to curing because of the high chain length/viscosity of thepolymer being used (when one considers the viscosity in the absence ofthe diluent). Such sealants provide an elongation at break ofsignificantly greater than 650%.

In one embodiment the process is used to prepare a one or two partorganopolysiloxane sealant composition. A two part composition comprisesin the first part diluted polymer and filler (when required) and in thesecond part catalyst and cross-linker are provided for mixing in anappropriate ratio (e.g. from 1:1 to 10:1) immediately prior to use.Additional additives to be discussed below may be provided in eitherpart 1 or part 2 of the part composition but are preferably added inpart two.

One particular problem which the silicone based sealant industry havehad to contend with is the production of a paintable cured sealantsurface. Typically this has not been possible with the vast majority ofcurrent cured silicone sealant formulations (if any in real terms).However, the applicants have found that highly filled sealantformulations comprising low levels (e.g. <15% by weight) of a highmolecular weight silicone polymer diluted in an organic compound arereadily paintable because of the low proportion of silicone compoundspresent in the formulation. This typically would not have been possiblebecause of the handling and mixing difficulties encountered with thesehigh molecular weight polymers as well as the poor elongation propertiesassociated with highly filled sealants. Tests suggest that saidpaintable sealant formulations are comparable if not an improvement overacrylic type fillers and because of their reduction in the amount ofsilicone present are of comparable price.

In an additional embodiment of the present invention there is provided amethod of producing a condensation cured silicone elastomer with asurface coated with a hardened protective coating comprising, exposing acomposition in accordance with process as hereinbefore described tomoisture until a cured elastomeric surface is obtained and a homogeneousdull surface develops, thereafter applying a protective coatingcomposition, hardenable at ambient conditions, over at least a portionof the cured elastomeric surface where the protective coatingcomposition wets the surface to which it is applied and produces anessentially flaw-free film and, thereafter, allowing the protectivecoating composition to harden.

A further advantage of polymers made by the process of the presentinvention is that they contain very low levels of cyclic siloxanes afterpolymerisation has completed.

In a further application of the present invention the diluted polymerresulting from the polymerisation process may be dispersed in a volatileor non-volatile low molecular weight organopolysiloxane containing fluidhaving a viscosity of between 4 and 100 mPa·s for use in personal careapplications. Preferably in this application the diluent is antrialkylsilyl terminated polydialkylsiloxane plasticiser.

The volatile silicone is appropriately a low viscosity dialkylsiloxane(typically a dimethylsiloxane) fluid which preferably containsdimethylsiloxane units and optionally trimethylsiloxane units andpreferably a viscosity of less than about 10 mPa·s at 25° C. The lowviscosity dialkylsiloxane fluid, may be either a cyclopolysiloxanehaving a degree of polymerisation of from 3 to 10 or a linear siloxanecompound having a degree of polymerisation of from 1 to 10, preferablybetween 1 and 5.

The cyclopolysiloxane compounds have been assigned the adopted name“CYCLOMETHICONE” by The Cosmetics, Toiletries and Fragrance Association,Inc., Washington, D.C. (CTFA). Both the cyclopolysiloxanes and thelinear siloxanes are clear fluids, and are essentially odourless,nontoxic, nongreasy and nonstinging. Cosmetically, these volatilealkylsilicone fluids are nonirritating to skin, and exhibit enhancedspreadability and ease of rub-out when applied. Once applied, thematerials evaporate leaving behind no residue.

Alkylsilicone fluids which are operable in accordance with the presentinvention leave substantially no residue after thirty minutes at roomtemperature when one gram of fluid is placed at the centre of a No. 1circular filter paper having a diameter of 185 mm supported at itsperimeter in open room atmosphere. Representative linear alkylsiliconefluids include hexamethyldisiloxane which has a boiling point of 99.5°C. and octamethyltrisiloxane which has a boiling point of 152° C.Representative cyclic alkylsilicone fluids suitable for the presentapplication include hexamethylcyclotrisiloxane which has a boiling pointof 133° C.; octamethylcyclotetrasiloxane which has a boiling point of171° C. and decamethylcyclopentasiloxane which has a boiling point of205° C. These alkylsilicone fluids may be used alone, or as mixtures incombinations of two or more of the individual fluids. Mixtures of thealkylsilicone fluids will result in a volatile material having anevaporating behaviour different from any one of the individualalkylsilicone fluids. The alkylsilicone fluids and their methods ofpreparation are known in the art, and such fluids are commerciallyavailable.

In some instances, it may be desirable to replace one or more of themethyl groups in the alkylsilicone fluid with other groups. Thus, theremay be substituted groups such as alkyl radicals having two to twelvecarbon atoms; aryl radicals having six to ten carbon atoms; aminegroups; vinyl; hydroxy; haloalkyl groups; aralkyl groups; and acrylategroups.

Compositions in accordance with the present invention comprising a blendof the diluted polymer dispersed in the alkylsilicone fluid mayadditionally contain a surfactant selected from the group consisting ofanionic and amphoteric surfactants. The surfactant system should providean acceptable level of foam on the hair and be capable of cleaning thehair, and may comprise one or more water soluble detergents, i.e., ananionic or amphoteric surfactant. Suitable anionic detergents includesulfonated and sulphated alkyl, aralkyl and alkaryl anionic detergents;alkyl succinates; alkyl sulfosuccinates and N-alkyl sarcosinates.Especially preferred are the sodium, magnesium, ammonium, and the mono-,di- and triethanolamine salts of alkyl and aralkyl sulphates as well asthe salts of alkaryl sulfonates. The alkyl groups of the detergentsgenerally have a total of from about 12 to 21 carbon atoms, may beunsaturated, and are preferably fatty alkyl groups. The sulphates may besulphate ethers containing one to ten ethylene oxide or propylene oxideunits per molecule. Preferably, the sulphate ethers contain 2 to 3ethylene oxide units.

Typical anionic detergents include, among others, sodium laurylsulphate, sodium lauryl ether sulphate, ammonium lauryl sulphate,triethanolamine lauryl sulphate, sodium C14-16 olefin sulfonate,ammonium pareth-25 sulphate (ammonium salt of a sulphated polyethyleneglycol ether of a mixture of synthetic C12-15 fatty alcohols), sodiummyristyl ether sulphate, ammonium lauryl ether sulphate, disodiummonooleamidosulfosuccinate, ammonium lauryl sulfosuccinate, sodiumdodecylbenzene sulfonate, triethanolamine dodecylbenzene sulfonate andsodium N-lauroyl sarcosinate. The most preferred anionic detergents arethe lauryl sulphates, particularly monoethanolamine, triethanolamine,ammonium and sodium lauryl sulphates. Sodium lauryl ether sulphate isalso very suitable for use in the compositions in accordance with thepresent invention.

Surfactants generally classified as amphoteric or ampholytic detergentsinclude, among others, cocoamphocarboxyglycinate,cocoamphocarboxypropionate, cocobetaine,N-cocamidopropyldimethylglycine, andN-lauryl-N-carboxymethyl-N-(2-hydroxyethyl)ethylenediamine. Othersuitable amphoteric detergents include the quaternary cycloimidates,betaines such as alpha-(tetradecyldimethylammonio)acetate,beta-(hexadecyldiethylammonio)propionate, andgamma-(dodecyldimethylammonio)butyrate., and sultaines such as3-(dodecyldimethylammonio)-propane-1-sulfonate, and3-(tetradecyldimethylammonio)ethane-1-sulfonate.

The compositions of this invention may contain a nonionic surfactant.The nonionic surfactants of the present invention are selected from thegroup consisting of fatty acid alkanolamide and amine oxide surfactants.The fatty acid alkanolamides are nonionic surfactants obtained byreacting alkanolamines such as monoethanolamine, diethanolamine,monoisopropanolamine, or diisopropanolamine with a fatty acid or fattyacid ester to form the amide. The hydrophobic portion of the nonionicsurfactant is provided by a fatty acid hydrocarbon chain which generallyhas from 10 to 21 carbon atoms. The fatty acid alkanolamide surfactantsinclude, for example, fatty acid diethanolamides such as isostearic aciddiethanolamide, lauric acid diethanolamide, capric acid diethanolamide,coconut fatty acid diethanolamide, linoleic acid diethanolamides,myristic acid diethanolamide, oleic acid diethanolamide, and stearicacid diethanolamide; fatty acid monoethanolamides such as coconut fattyacid monoethanolamide; and fatty acid monoisopropanolamides such asoleic acid monoisopropanolamide and lauric acid monoisopropanolamide.

The amine oxides are well known nonionic surfactants usually obtained byoxidizing a tertiary amine to form the amine oxide. They are sometimesalso referred to as polar nonionic surfactants. Amine oxide surfactantsinclude, for example, the N-alkyl amine oxides such asN-cocodimethylamine oxide, N-lauryl dimethylamine oxide, N-myristyldimethylamine oxide, and N-stearyl dimethylamine oxide; the N-acyl amineoxides such as N-cocamidopropyl dimethylamine oxide andN-tallowamidopropyl dimethylamine oxide; and N-alkoxyalkyl amine oxidessuch as bis(2-hydroxyethyl) C12-15 alkoxy-propylamine oxide. Thehydrophobic portion of the amine oxide surfactants is generally providedby a fatty hydrocarbon chain containing from 10 to 21 carbon atoms.

For purposes of this invention the alkanolamide and amine oxidesurfactants are preferred. In general, the fatty acid diethanolamidesand N-alkyl dimethylamine oxides are preferred for use in thecompositions. Especially preferred are the fatty acid diethanolamidesand N-alkyl dimethylamine oxides where the fatty hydrocarbon chaincontains from 10 to 18 carbon atoms. For example, especially preferrednonionic surfactants include lauric acid diethanolamide, N-lauryldimethylamine oxide, coconut acid diethanolamide, myristic aciddiethanolamide, and oleic acid diethanolamide.

Additional categories of surfactant materials may also be included suchas cationic and zwitterionic surfactants, and representative compoundsare set forth in detail in U.S. Pat. No. 4,902,499, issued Feb. 20,1990, which is considered to be incorporated herein by reference.

Other adjuvants may be added to compositions in accordance with thepresent invention comprising a blend of the diluted polymer dispersed inthe alkylsilicone fluid include for example thickeners, perfumes,colorants, electrolytes, pH control ingredients, foam boosters and foamstabilizers, antimicrobials, antioxidants, ultraviolet light absorbersand medicaments. For example, it is sometimes preferred to employ athickener in the compositions to facilitate the hand application of thecomposition to the hair. Thickeners are preferably used in sufficientquantities to provide a more luxurious effect. For example, viscositieswithin the range of 6,000 to 12,000 mPa·s measured at 25° C. Suitablethickeners, include, among others, sodium alginate, gum arabic,polyoxyethylene, guar gum, hydroxypropyl guar gum, cellulose derivativessuch as methylcellulose, methyl hydroxypropylcellulose,hydroxypropylcellulose, polypropylhydroxyethylcellulose, starch andstarch derivatives such as hydroxyethylamylose, and starch amylose,locust bean gum, electrolytes such as sodium or ammonium chloride,saccharides such as fructose and glucose, and derivatives of saccharidessuch as PEG-120 methyl glucose dioleate.

The perfumes which can be used in the compositions are cosmeticallyacceptable perfumes. Colorants are used to confer a colour to thecomposition and may generally be used. Although not required, it ispreferred to employ an acid to adjust the pH within the range of 5 to 9or more preferably within the range of 6 to 8 in the compositions ofthis invention. Any water soluble acid such as a carboxylic acid or amineral acid is suitable. For example, suitable acids include mineralacids such as hydrochloric, sulphuric, and phosphoric, monocarboxylicacids such as acetic acid, lactic acid, or propionic acid; andpolycarboxylic acids such as succinic acid, adipic acid and citric acid.

If for special purposes additional conditioners are desired, they may beadded. For example, any of the well-known organic cationic hairconditioning components may be added. Some cationic conditioningcomponents that may be used in the present invention to provide hairgrooming include quaternary nitrogen derivatives of cellulose ethers,homopolymers of dimethyldiallyl-ammonium chloride, copolymers ofacrylamide and dimethyldiallylammonium chloride, homopolymers orcopolymers derived from acrylic acid or methacrylic acid containingcationic nitrogen functional groups attached to the polymer via ester oramide linkages, polycondensation products ofN,N′-bis-(2,3-epoxypropyl)-piperazine or of piperazine-bis-acrylamideand piperazine, poly-(dimethylbutenylammonium chloride)-.alpha,omega.-bis-(triethanol-ammonium) chloride, and copolymers ofvinylpyrrolidone and acrylic acid esters with quaternary nitrogenfunctionality. The above cationic organic polymers and others aredescribed in more detail in U.S. Pat. No. 4,240,450 which is herebyincorporated by reference to further describe the cationic organicpolymers. Other categories of conditioners such as monomeric quaternaryamine salts may also be employed.

A preservative may be required and representative preservatives whichmay be employed include about 0.1-0.2 weight percent of compounds suchas formaldehyde, dimethyloldimethylhydantoin,5-bromo-5-nitro-1,3-dioxane, methyl- and propyl para-hydroxybenzoates,and mixtures of such benzoates with sodium dehydroacetate, sorbic acid,and imidazolidinyl urea.

Compositions in accordance with the present invention comprising a blendof the diluted polymer dispersed in the alkylsilicone fluid mayadditionally contain may also be formulated to include dyes, colorants,reducing agents, neutralizing agents, and preservatives, necessary fortheir application as permanent wave systems or hair dyes, for example.The active formulation can be applied in several different formsincluding lotions, gels, mousses, aerosols, and pump sprays, forexample, and as conditioners and shampoos. The active ingredient mayinclude a carrier, and suitable carrier fluids for hair careformulations are water as well as, for example, such fluids as alcoholsnamely ethanol or isopropanol, hydrocarbons and halogenated hydrocarbonsas mineral spirits and trichloroethane, cyclic siloxanes, and aerosolpropellants.

When the composition is intended for aerosol application, propellantgases can be included such as carbon dioxide, nitrogen, nitrous oxide,volatile hydrocarbons such as butane, isobutane, or propane andchlorinated or fluorinated hydrocarbons such as dichlorodifluoromethaneand dichlorotetrafluoroethane or dimethylether.

Resulting products may be in the form of ointments, creams, gels,pastes, foams, aerosols and the like. They may be present inpharmaceutical, medical and/or therapeutic applications analgesic;anaesthetic; anti-acne; antibacterial; anti-yeast; antifungal;antivirals; antidandruff; antidermatitis; antipruritic; antiemetic;anti-motion sickness; anti-inflammatory; antihyperkeratolytic; anti-dryskin; antiperspirant; antipsoriatic; antiseborrheic; hair conditioning;hair treatment; anti-aging; antiwrinkle; anti-asthmatic; bronchodilator;sunscreen; antihistamine; skin-lightening; depigmenting; wound-healing;vitamin; corticosteroid; tanning or hormonal. Products of this type arecommonly used include hair care products such as shampoos, hairconditioners, hair colorants, hairstyling preparations, such as settinglotions and hairsprays and permanent wave preparations, skin careproducts such as facial or body powders, blushers, eyeshadows,eyeliners, bath grains or pellets, lipsticks, moisturisers, cosmetics,hand and body lotions, concealers, compact powders, foundations and suncare products such as sun screen formulations

In a still further embodiment of the present invention a diluted polymerin accordance with the present invention may be incorporated into a highviscosity silicone rubber composition

In accordance with the present invention there is provided a method ofmaking a silicone rubber composition comprising the steps of:—

-   Preparing a diluted organopolysiloxane containing polymer as    hereinbefore described optionally with an alkenyl group, condensable    group, silyl-hydride or trimethylsilyl containing end-blocker and    with a siloxane based diluent; compounding the resulting diluted    organopolysiloxane polymer with

one or more reinforcing and/or non reinforcing fillers and

a curing agent.

In the present embodiment any filler or combination of fillers ashereinbefore described may be utilised. Usually the filler content ofthe composition will reside within the range from about 5 to about 200parts by weight per 100 parts by weight of the polymer excluding thediluent portion.

A curing agent, as noted above, is required and compounds which can beused herein include organic peroxides such as dialkyl peroxides,diphenyl peroxides, benzoyl peroxide, 1,4-dichlorobenzoyl peroxide,2,4-dichlorobenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide,tertiary butyl-perbenzoate, monochlorobenzoyl peroxide, ditertiary-butylperoxide, 2,5-bis-(tertiarybutyl-peroxy)-2,5-dimethylhexane,tertiary-butyl-trimethyl peroxide,tertiary-butyl-tertiary-butyl-tertiary-triphenyl peroxide,1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, and t-butylperbenzoate. The most suitable peroxide based curing agents are benzoylperoxide, 2,4-dichlorobenzoyl peroxide, di-t-butyl peroxide, and dicumylperoxide. Such organic peroxides are used at up to 10 parts per 100parts of the combination of polymer, filler and optional additives.Preferably between 0.2 and 2 parts of peroxide are used.

The present compositions can also be cured and/or cross-linked by ahydrosilylation reaction catalyst in combination with anorganohydrogensiloxane as the curing agent instead of an organicperoxide, providing a majority of polymer molecules which contain atleast two unsaturated groups suitable for cross-linking with theorganohydrogensiloxane. These groups are typically alkenyl groups, mostpreferably vinyl groups. To effect curing of the present composition,the organohydrogensiloxane must contain more than two silicon bondedhydrogen atoms per molecule. The organohydrogensiloxane can contain, forexample, from about 4-20 silicon atoms per molecule, and have aviscosity of up to about 10 Pa·s at 25° C. The silicon-bonded organicgroups present in the organohydrogensiloxane can include substituted andunsubstituted alkyl groups of 1-4 carbon atoms that are otherwise freeof ethylenic or acetylenic unsaturation.

For the purpose of this application “Substituted” means one or morehydrogen atoms in a hydrocarbon group has been replaced with anothersubstituent. Examples of such substituents include, but are not limitedto, halogen atoms such as chlorine, fluorine, bromine, and iodine;halogen atom containing groups such as chloromethyl, perfluorobutyl,trifluoroethyl, and nonafluorohexyl; oxygen atoms; oxygen atomcontaining groups such as (meth)acrylic and carboxyl; nitrogen atoms;nitrogen atom containing groups such as amino-functional groups,amido-functional groups, and cyano-functional groups; sulphur atoms; andsulphur atom containing groups such as mercapto groups.

Preferably the hydrosilylation catalyst may be any hydrosilylationcatalyst hereinbefore described but is preferably a platinum basedcatalyst.

The hydrosilylation catalyst may be added to the present composition inan amount equivalent to as little as 0.001 part by weight of elementalplatinum group metal, per one million parts (ppm) of the composition.Preferably, the concentration of the hydrosilylation catalyst in thecomposition is that capable of providing the equivalent of at least 1part per million of elemental platinum group metal. A catalystconcentration providing the equivalent of about 3-50 parts per millionof elemental platinum group metal is generally the amount preferred.

The curing agent may alternatively be a condensation reaction catalystbecause the present compositions may alternatively be cured and/orcross-linked by a condensation reaction in combination with a siloxaneand/or silane cross-linker having at least two and preferably at leastthree groups reactable with hydroxyl or hydrolysable groups provided amajority of polymer molecules contain at least two condensable groups ashereinbefore described suitable for reaction with said cross-linker.

Optional additives for a high consistency rubber composition maycomprise one or more of the following rheology modifiers, pigments,colouring agents, anti-adhesive agents adhesion promoters, heatstabilisers, blowing agents, flame retardants, electrically and/orthermally conductive fillers, and desiccants, each of which arepreferably as hereinbefore described.

Other optional ingredients which may be incorporated in the compositionof a high consistency silicone rubber include handling agents, peroxidecure co-agents, acid acceptors, and UV stabilisers.

Handling agents are used to modify the uncured properties of thesilicone rubber such as green strength or processability sold under avariety of trade names such as SILASTIC® HA-1, HA-2 and HA-3 sold by DowCorning corporation)

Peroxide cure co-agents are used to modify the properties, such astensile strength, elongation, hardness, compression set, rebound,adhesion and dynamic flex, of the cured rubber. These may include di- ortri-functional acrylates such as Trimethylolpropane Triacrylate andEthylene Glycol Dimethacrylate; Triallyl Isocyanurate, TriallylCyanurate, Polybutadiene oligomers and the like. Silyl-hydridefunctional siloxanes may also be used as co-agents to modify theperoxide catalysed cure of siloxane rubbers.

The acid acceptors may include Magnesium oxide, calcium carbonate, Zincoxide and the like.

The ceramifying agents can also be called ash stabilisers and includesilicates such as wollastonite.

The silicone rubber composition in accordance with this embodiment maybe made by any suitable route, for example one preferred route is tofirst make a silicone rubber base by heating a mixture of fumed silica,a treating agent for the silica, and the diluted organopolysiloxanepolymer of the present invention. The silicone rubber base is removedfrom the first mixer and transferred to a second mixer where generallyabout 150 parts by weight of a non-reinforcing or extending filler suchas ground quartz is added per 100 parts by weight of the silicone rubberbase. Other additives are typically fed to the second mixer such ascuring agents, pigments and colouring agents, heat stabilizers,anti-adhesive agents, plasticizers, and adhesion promoters. In a secondpreferred route the diluted organopolysiloxane polymer of the presentinvention and any desired filler plus any desired treating agent are fedinto a reactor and mixed, further additives as described above includingcure agents are then fed into the same reactor and further mixed.

Other potential applications of the present invention include use of thediluted polymer in hot melt adhesives, pressure sensitive adhesives, inencapsulants for solar cells and any other applications requiring theuse of organopolysiloxane gums.

The invention will now be described by way of Example. For the sake ofcomparison the diluent used in both examples was a commerciallyavailable processing aid called HYDROSEAL® G250H, a hydrotreated mineraloil cut (n-para 7%/iso-para 51% and naphthenic 42%) produced by TotalFina.

EXAMPLE 1 Chain Extension Using a Dibutylacetoxysilane

Production of the Polymer

50 g of dimethylhydroxy terminated polydimethylsiloxane having aviscosity of 80,000 mPa·s at 25° C. was placed in a suitable container.0.2 g of dibutoxydiacetoxysilane (DBDAc) and 500 ppm weight (in relationto the polymer) of dibutyltindiacetate catalyst were added together witha stoichiometric quantity of water to hydrolyze the acetoxy groups onthe DBDAc. As soon as an initial viscosity increase in viscosity wasdetected 50 g of processing aid were introduced into the reactionmixture and the variation in viscosity was tracked until the viscosityof the product reached a maximum.

Sealant Formulation

The resulting polymer sealant is formulated with 86.485% weight polymerproduced as described above, 5% weight of a 50% mixture of methyltriacetoxysilane and ethyl triacetoxysilane cross-linker, 8% weight offumed silica, 0.5% weight of Poly (PO)(EO) (rheology modifier) and0.015% of dibutyltindiacetate catalyst. The sealant properties are shownin Table 1.

Adhesion test (7dRT) was carried out to show that a bead of sealantsuccessfully bonded to a standard glass plate after being allowed tocure at 23° C. and 50% relative humidity for 7 days. Adhesion wasassessed by subsequent to the curing period the beads were pulled at 90°and the failure was rated as follows:

0: adhesive failure—poor adhesion)

1: boundary or mixed mode (adhesive/cohesive) failure—acceptableadhesion.

2: cohesive failure—excellent adhesion

Adhesion test (7H₂O) was carried out to show that a bead of sealantsuccessfully bonded to a standard glass plate after being allowed tocure at 23° C. and 50% relative humidity for 7 days and thensubsequently 7 days in water. The bead of sealant was pulled as inadhesion test (7dRT).

The cure in depth tests were undertaken to determine how far below thesurface the sealant had hardened in 24 and 72 hours by filling asuitable container (avoiding the introduction of air pockets) withsealant, curing the sealant contained in the container for theappropriate period of time at room temperature (about 23° C.) and about50% relative humidity. After the appropriate curing time the sample isremoved from the container and the height of the cured sample ismeasured.

TABLE 1 Standards properties Test method Tack Free Time (min) ASTMD2377-94 24 Penetration (mm/10 * 3 sec) ASTM D217-97 170 Cure in depth24 h 1.5 (mm/24 h) Cure in depth 72 h 1.7 (mm/72 h) Specify gravity(kg/l) ASTM D1475-98 0.94 Tensile Strength ASTM D412-98a 0.6 (sheet 2 mm) (MPa) Elongation at break (%) ASTM D412-98a 1047 100% modulus (MPa)ASTM D638-97 0.13 Hardness (Shore A) ASTM D2240-97 5 Adhesion Tests 7dRT7H₂O glass 2 2

1. A method of making a diluted chain extended organopolysiloxanecontaining polymer comprising the steps of: (a) reacting a pre-formedpolymer with a chain extender reactable with terminal groups of thepolymer, said chain extender being selected from the group of (v) adihydrosilane; and (vii) a polydialkylsiloxane having a degree ofpolymerisation of from 2 to 25 and at least one Si—H bond per terminalgroup; in the presence of a diluent material, a suitable catalyst andoptionally an end-blocking agent; and (b) where required quenching thechain extension process; wherein the diluent material is substantiallyretained within the resulting diluted organopolysiloxane containingpolymer; and wherein the diluent material is selected from one or moreof the group of a trialkylsilyl terminated polydialkyl siloxane whereeach alkyl group may be the same or different and comprises from 1 to 6carbon atoms, polyisobutylenes (PIB), phosphate esterspolyalkylbenzenes, and linear and/or branched alkylbenzenes esters ofaliphatic monocarboxylic acids; or wherein the diluent material isselected from one or more of the group comprising linear or branchedmono unsaturated hydrocarbons; and mineral oil fractions comprisinglinear (n-paraffinic) mineral oils, branched (iso-paraffinic) mineraloils, cyclic (naphthenic) mineral oils, and mixtures thereof.
 2. Amethod in accordance with claim 1 wherein the preformed polymer has thegeneral formulaX¹-A-X² where X¹ and X² are independently selected from silyl groupscontaining at least one unsaturated substituent and A is selected fromthe group of a siloxane polymeric chain, a siloxane copolymeric chainand a siloxane/organic block copolymeric chain and the chain extendercomprises two Si—H bonds adapted to be reactable with the unsaturatedsubstituent in X¹ and X².
 3. A diluted chain extended organopolysiloxanecontaining polymer obtained by the method in accordance with claim 1wherein said diluent material is substantially retained within saiddiluted chain extended organopolysiloxane containing polymer.
 4. Amethod of making a curable composition capable of cure to an elastomericbody comprising the steps of mixing a diluted chain extendedorganopolysiloxane containing polymer comprising condensable groupsobtained in accordance with claim 1 with a suitable cross-linking agentwhich is reactive with the diluted chain extended organopolysiloxanecontaining polymer, a suitable condensation catalyst and optionallyfiller.
 5. A method of making a curable composition capable of cure toan elastomeric body in accordance with claim 4 wherein the cross-linkingagent is one or more silanes or siloxanes which contain acyloxy groups,ketoximino groups and the catalyst is a tin catalyst.
 6. A method ofmaking a curable composition capable of cure to an elastomeric body inaccordance with claim 4 wherein the cross-linking agent is one or moresilanes or siloxanes which contain alkoxy groups and alkenyloxy groupsand the catalyst is a titanate or zirconate or a chelated titanate orzirconate.
 7. A method of making a curable composition capable of cureto an elastomeric body in accordance with claim 4 wherein the fillercomprises one or more finely divided, reinforcing fillers selected fromthe group of high surface area fumed silica, precipitated silica, andcalcium carbonate, and/or one or more extending fillers selected fromthe group of crushed quartz, diatomaceous earth, barium sulphate, ironoxide, titanium dioxide, carbon black, talc, and wollastonite.
 8. Acomposition comprising a diluted chain extended organopolysiloxanecontaining polymer obtained in accordance with the method of claim 1wherein said diluent material is substantially retained within thediluted chain extended organopolysiloxane containing polymer and whereinadditional diluent comprising a volatile or non-volatile low molecularweight organopolysiloxane containing fluid having a viscosity of between4 and 100 mPa·s at 25° C. is added to the composition subsequent tocompletion of polymerisation.
 9. A method of making a silicone rubbercomposition comprising the steps of: preparing a dilutedorganopolysiloxane containing polymer in accordance with claim 1optionally with an alkenyl group, a condensable group, a silyl-hydrideor trimethylsilyl containing end-blocker, and a diluent; and compoundingthe resulting diluted organopolysiloxane polymer with one or morereinforcing and/or non reinforcing fillers and a curing agent; andoptional additives selected from the group of one or more rheologymodifiers, pigments, colouring agents, anti-adhesive agents, adhesionpromoters, blowing agents, fire retardants and dessicants.
 10. A methodin accordance with claim 9 wherein the polymer comprises unsaturatedgroups and the curing agent is a hydrosilylation reaction catalyst incombination with an organohydrogensiloxane.
 11. A method in accordancewith claim 10 wherein the organohydrogensiloxane comprises from 4-20silicon atoms per molecule, and has a viscosity of up to about 10 Pa·sat 25° C.
 12. A method in accordance with claim 10 wherein thehydrosilylation catalyst is a platinum group metal based catalystselected from a platinum, rhodium, iridium, palladium or rutheniumcatalyst.
 13. A method as set forth in claim 1 wherein the end-blockingagent is further defined as providing a functional group to the dilutedchain extended organopolysiloxane containing polymer wherein thefunctional group is selected from the group of —SiOH₃, —(R^(a))Si(OH)₂,—(R^(a))₂SiOH, —R^(a)Si(OR^(b))₂, —Si(OR^(b))₃, —R^(a) ₂SiOR^(b) or—R^(a) ₂Si—R^(c)— SiR^(d) _(p)(OR^(b))_(3-p) wherein each R^(a) isindependently a monovalent hydrocarbyl group, wherein each R^(b) isindependently an alkyl group having up to 6 carbon atoms and each R^(d)is independently an alkyl or alkoxy group in which the alkyl group hasup to 6 carbon atoms, wherein each R^(c) is a divalent hydrocarbon groupwhich is optionally interrupted by one or more siloxane spacers havingup to six silicon atoms, and wherein p is 0, 1, or
 2. 14. A method asset forth in claim 9 wherein the diluent is further defined as asiloxane-based diluent.
 15. A method of making a curable compositioncapable of cure to an elastomeric body comprising the steps of (a)reacting a pre-formed polymer with a chain extender reactable withterminal groups of the polymer, said chain extender being selected fromthe group of (v) a dihydrosilane; and (vii) a polydialkylsiloxane havinga degree of polymerisation of from 2 to 25 and at least one Si—H bondper terminal group; in the presence of a diluent material, a suitablecatalyst and optionally an end-blocking agent; and (b) where required,quenching the chain extension process, to make a diluted chain extendedorganopolysiloxane containing polymer comprising condensable groupswherein the diluent material is substantially retained within theorganopolysiloxane containing polymer; and (c) mixing theorganopolysiloxane containing polymer with a suitable cross-linkingagent which is reactive with the organopolysiloxane containing polymer,a suitable condensation catalyst and optionally filler.
 16. Acomposition comprising a diluted chain extended organopolysiloxanecontaining polymer formed by a method comprising the steps of: (a)reacting a pre-formed polymer with a chain extender reactable withterminal groups of the polymer, said chain extender being selected fromthe group of (v) a dihydrosilane; and (vii) a polydialkylsiloxane havinga degree of polymerisation of from 2 to 25 and at least one Si—H bondper terminal group; in the presence of a diluent material, a suitablecatalyst and optionally an end-blocking agent; and (b) where requiredquenching the chain extension process; wherein the diluent material issubstantially retained within the resulting chain extendedorganopolysiloxane containing polymer; and wherein additional diluentcomprising a volatile or non-volatile low molecular weightorganopolysiloxane containing fluid having a viscosity of between 4 and100 mPa·s at 25° C. is added to the composition subsequent to completionof polymerisation.
 17. A method of making a silicone rubber compositioncomprising the steps of: preparing a diluted organopolysiloxanecontaining polymer optionally with an alkenyl group, a condensablegroup, a silyl-hydride or trimethylsilyl containing end-blocker, and adiluent, by (a) reacting a pre-formed polymer with a chain extenderreactable with terminal groups of the polymer, the chain extender beingselected from the group of (v) a dihydrosilane; and (vii) apolydialkylsiloxane having a degree of polymerisation of from 2 to 25and at least one Si—H bond per terminal group; in the presence of adiluent material, a suitable catalyst and optionally an end-blockingagent; and (b) where required quenching the chain extension process;wherein the diluent material is substantially retained within theresulting diluted organopolysiloxane containing polymer; and compoundingthe resulting diluted organopolysiloxane polymer with one or morereinforcing and/or non reinforcing fillers and a curing agent; andoptional additives selected from the group of one or more rheologymodifiers, pigments, colouring agents, anti-adhesive agents, adhesionpromoters, blowing agents, fire retardants and dessicants.